S-(alpha, alpha&#39;-disubstituted-alpha&#34;-acetic acid) substituted dithiocarbonate derivatives for controlled radical polymerizations, process and polymers made therefrom

ABSTRACT

Dithiocarbonate derivatives are disclosed, along with a process for preparing the same. The dithiocarbonate compounds can be utilized as initators, chain transfer agents and/or terminators in controlled free radical polymerizations. The dithiocarbonates can be used to produce polymers having narrow molecular weight distribution. Advantageously, the compounds of the present invention can also introduce functional groups into the resulting polymers. The dithiocarbonate compounds have low odor and are substantially colorless.

CROSS REFERENCE

[0001] This patent application is a continuation-in-part applicationbased on U.S. application Ser. No. 10/278,335 filed Oct. 23, 2002 forS-(α,α′-Disubstituted-α″-Acetic Acid) Substituted DithiocarbonateDerivatives For Controlled Radical Polymerizations, Process And PolymerMade Therefrom, which is a continuation-in-part application based onU.S. application Ser. No. 09/505,749 filed Feb. 16, 2000 forS,S′-Bis-(α,α′-Disubstituted-α″-Acetic Acid)-Trithiocarbonates AndDerivatives As Initiator-Chain Transfer Agent-Terminator For ControlledRadical Polymerizations And The Process For Making The Same.

FIELD OF THE INVENTION

[0002] The present invention relates tos,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonates andderivatives thereof, as well as a process for making the same. Moreover,other functional end groups can be derived from the carboxylic acid endgroups. The compounds can be utilized as initiators, chain transferagents, or terminators for controlled free radical polymerizations. Freeradical polymerizations utilizing s,s′-bis-(α,α′disubstituted-α″-aceticacid)-trithiocarbonate compounds generally form telechelic polymers. Ifan initiator other than the s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate compound is also utilized, a polymer having asingle functional end group is formed in proportion to the amount of theinitiator to the s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate compound utilized.

[0003] In a further embodiment, dithiocarbonate derivatives aredisclosed, along with a process for preparing the same. Thedithiocarbonate compounds can be utilized as initators, chain transferagents and/or terminators in controlled free radical polymerizations.The dithiocarbonates can be used to produce polymers having narrowmolecular weight distribution. Advantageously, the compounds of thepresent invention can also introduce functional groups into theresulting polymers. The dithiocarbonate compounds have low odor and aresubstantially colorless.

BACKGROUND OF THE INVENTION

[0004] Although several members of the class of organic thiocarbonateshave been known for many years and various routes have been employed fortheir synthesis, the s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate compounds of the present invention have not beendisclosed. Trithiocarbonate compounds have been claimed for variousapplications, such as pesticides for agriculture, and also aslubricating oil additives.

[0005] Traditional methods of producing block copolymers, such as byliving polymerization or the linking of end functional polymers, suffermany disadvantages, such as the restricted type monomers which can beutilized, low conversion rates, strict requirements on reactionconditions, and monomer purity. Difficulties associated with end linkingmethods include conducting reactions between polymers, and problems ofproducing a desired pure end functional polymer. Thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundsof the present invention can alleviate the above noted problems anddifficulties when utilized in free radical polymerizations.

[0006] The prior art WO98/01478 reference discloses the use ofthiocarbonates to conduct living free radical polymerizations. Thereference is limited to alkyl and benzyl functional groups, and isunable to make any aryl or carboxylic acid substituted trithiocarbonateswith general methods known to the art. Synthesis, p 894 (1986), J.Chemical Research (Synopsis), p 478 (1995), and SyntheticCommunications, Vol. 18, p 1531 (1988). We have also found theconversion for the dibenzyl derivatives disclosed in their example 26 tobe very slow compared to the present invention when polymerizingacrylate, as can be seen in the Example section of this application. TheWO/01478 reference states in the background that experiments have shownthat dithiocarbamate derivatives have low transfer constants and aresubstantially ineffective in conferring living characteristics toradical polymerizations.

[0007]Macromolecules, 32, p 6977-6980 (1999) states that

[0008] dithiocarbamate compounds:

[0009] cannot control polymerization and are not effective RAFT agents.Additionally, carboxyl end groups cannot be formed utilizing theprocesses disclosed. Also WO 99/35177 and Macromolecules, RapidCommunications, 21, p 1035-1039 (2001) finds that R, R¹, and R² need tobe fine tuned to control polymerization, meaning there is no guaranteeall dialkyl dithiocarbamate will work as RAFT agents. Moreover, thesubstituent of the single bonded sulfur atom cannot be a carboxylic acidcontaining group in their synthesis.

[0010] U.S. Pat. No. 6,153,705 relates to a process for polymerizingblock polymers of general formula (I):

[0011] in which process the following are brought into contact with eachother:

[0012] an ethylenically unsaturated monomer of formula:

CYY′(═CW—CW′)_(a)═CH₂,

[0013] a precursor compound of general formula (II):

[0014] and a radical polymerization initiator.

[0015] Macromolecule Rapid Communications 2001, 22, p 1497-1503 and U.S.Pat. No. 6,153,705 disclose various xanthate compounds. The referencescannot prepare the xanthate compounds of the present invention utilizingthe methods disclosed within the references. 1) Alkylation with tertiaryalkyl halides disclosed in the '705 patent will result in elimination,not substitution. The -halo-′, ″-dialkylacetic acid disclosed by thereference cannot be alkylated. 2) The compounds of the present inventioncontain a tertiary carbon attached to the single bonded sulfur atom ofthe compound. The '705 patent preferably utilizes an R¹ group having asecondary carbon atom which results in a lower chain transfercoefficient than the present invention. Moreover, the xanthatesdisclosed by the references have been found to be less effective.

[0016] Unexpectedly, in view of the prior art, the compounds of thepresent invention are able to confer living characteristics to a freeradical polymerization.

SUMMARY OF THE INVENTION

[0017] The present invention relates tos,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonates whichhave the general formula:

[0018] where R¹ and R² are set forth below, to derivatives thereof, andto a process for making the same.

[0019] The s,s′-bis-(α,α′-disubstituted-α″-acetic acid) trithiocarbonatecompounds can generally be formed from carbon disulfide, a haloform, anda ketone in a strong base, such as sodium hydroxide, followed byacidification. The s,s′-bis-(α,α′-disubstituted-α″-acetic acid)trithiocarbonate compounds can be used as inifertors, i.e. as initiatorsand chain transfer agents, and/or chain terminators or as achain-transfer agent during polymerization. The compounds can thus beutilized to control free radical polymerization thermally and chemicallyto give narrow molecular weight distributions. Polymerization ofmonomers can be in bulk, in emulsion, or in solution. Block copolymerscan be made if two or more monomers are polymerized in succession. Thedifunctional acid end groups present can further react with otherreactive polymers or monomers to form block or random copolymers. Freeradical polymerizations utilizing thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundsgenerally form telechelic polymers. If an initiator other than thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundis also utilized, a polymer having a single functional end group isformed in proportion to the amount of said other initiator to thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundutilized.

[0020] In a further embodiment, dithiocarbonate compounds of the presentinvention have the general formulae:

[0021] wherein T, R¹², R¹³, R¹⁴, a and j are defined hereinbelow.Preferably, the substituent T is an amine derivative, preferably adialkylamino derivative. Thus, the dithiocarbonate compounds arexanthate and dithiocarbamate derivatives. A process for preparing thedithiocarbonate compounds is disclosed.

[0022] The dithiocarbonate compounds can be utilized as chain transferagents in free radical polymerizations, as well as initiators and/orchain terminators. Narrow molecular weight distribution polymers canadvantageously be produced with the dithiocarbonates of the presentinvention. The polymers formed in the presence of the dithiocarbonatecompounds have at least one terminal carboxyl group which can be furtherreacted to form block or random copolymers. The monomers or polymerspolymerized onto the dithiocarbonate compounds are added between thesingle bonded sulfur atom and the adjacent tertiary carbon atom. Thepolymerizations are conducted under inert atmospheres. The compoundsand/or the polymers or copolymers of the present invention can be madewater soluble or water dispersible through their metal or ammonium saltsof the carboxylic acid group.

[0023] Accordingly, polymers having the following formulae can beproduced utilizing the dithiocarbonate compounds of the presentinvention:

[0024] wherein, T, R¹², R¹³, R¹⁴, polymer, a, g, j and f are definedhereinbelow.

DETAILED DESCRIPTION OF THE INVENTION

[0025] The s,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonateand derivatives prepared by the processes disclosed later hereingenerally can be described by the formula:

[0026] wherein R¹ and R², independently, can be the same or different,and can be linear or branched alkyls having from 1 to about 6 carbonatoms, or a C₁ to about C₆ alkyl having one or more substituents, or oneor more aryls or a substituted aryl group having 1 to 6 substituents onthe aryl ring, where the one or more substituents, independently,comprise an alkyl having from 1 to 6 carbon atoms; or an aryl; or ahalogen such as fluorine or chlorine; or a cyano group; or an etherhaving a total of from 2 to about 20 carbon atoms such as methoxy, orhexanoxy; or a nitro; or combinations thereof. Examples of suchcompounds include s,s′-bis-2-methyl-2-propanoic acid-trithiocarbonateand s,s′-bis-(2-phenyl-2-propanoic acid)-trithiocarbonate. R¹ and R² canalso form or be a part of a cyclic ring having from 5 to about 12 totalcarbon atoms. R¹ and R² are preferably, independently, methyl or phenylgroups.

[0027] The abbreviated reaction formula for thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonates of thepresent invention can be generally written as follows:

[0028] The process utilized to form thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundsof the present invention is generally a multi-step process and includescombining the carbon disulfide and a base whereby an intermediatetrithio structure is formed, see I, II, III, and IV. Ketone can serve assolvent for the carbon disulfide/base reaction and thus can be added inthe first step of the reaction. In the second step of the reaction, thehaloform, or haloform and ketone, or a α-trihalomethyl-α-alkanol areadded to the trithio intermediate mixture and reacted in the presence ofadditional base, see V, VI, and VII. The formed reaction product, seeIX, is subsequently acidified, thus completing the reaction and formingthe above described s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate compound, see X.

[0029] The reaction is carried out at a temperature sufficient tocomplete the interaction of the reactants so as to produce thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundin a desired time. The reaction can be carried out at any temperaturewithin a wide range from about the freezing point of the reaction massto about the reflux temperature of the solvent. The reaction temperatureis generally from about minus 15° C. to about 80° C., desirably fromabout 0° C. to about 50° C., and preferably from about 15° C. to about35° C., with room temperature being preferred. The reaction can beperformed at atmospheric pressure. The reaction time depends uponseveral factors, with the temperature being most influential. Thereaction is generally complete within 20 hours and preferably within 10hours.

[0030] A phase transfer catalyst is preferably utilized if a solvent isused in the reaction. Examples of solvents are set forth herein below.The ketone utilized in the reaction may double as a solvent, andtherefore no catalyst usually is needed. The amount of phase transfercatalyst, when utilized in the present invention, is generally fromabout 0.1 mole percent to about 10 mole percent, desirably from about0.5 mole percent to about 5 mole percent and preferably from about 2mole percent to about 4 mole percent per mole of carbon disulfide. Thephase transfer catalysts can be polyether, and/or an onium saltincluding a quaternary or tertiary organic compound of a group VA or VIAelement of the Periodic Table and salts thereof. Most preferred arequaternary amines, and salts thereof.

[0031] “Onium salts” more particularly refer to tertiary or quaternaryamines and salts such as are generally used in the phase transfercatalysis of heterogeneous reaction in immiscible liquids. The generalrequirement for the onium salt chosen is that it be soluble in both theorganic and aqueous phases, when these two liquid phases are present,and usually a little more soluble in the organic phase than the aqueousphase. The reaction will also proceed with a phase transfer catalystwhen there is only a single organic liquid phase present, but such areaction is less preferable than one in which both aqueous and organicliquid phases are present. A wide variety of onium salts is effective inthis ketoform synthesis.

[0032] The onium salts include the well-known salts, tertiary amines andquaternary compounds of group VA elements of the Periodic Table, andsome Group VIA elements such as are disclosed in the U.S. Pat. No.3,992,432 and in a review in Angewandte Chemie, International Edition inEnglish, 16 493-558 (August 1977). Discussed therein are various aniontransfer reactions where the phase transfer catalyst exchanges itsoriginal ion for other ions in the aqueous phase, making it possible tocarry our chemistry there with the transported anion, including OH-ions.

[0033] The onium salts used in this synthesis include one or more groupshaving the formula (R_(n)Y)⁺X⁻, wherein Y is either a pentavalent ionderived from an element of Group VA, or a tetravalent ion derived froman element of Group VIA; R is an organic moiety of the salt moleculebonded to Y by four covalent linkages when Y is pentavalent, and threecovalent linkages when Y is tetravalent; X⁻ is an anion which willdissociate from the cation (R_(n)Y)⁺ in an aqueous environment. Thegroup (R_(n)Y)⁺X⁻ may be repeated as in the case of dibasic quaternarysalts having two pentavalent Group VA ions substituted in the mannerdescribed.

[0034] The preferred onium salts for use in the invention have theformula

(R^(A)R^(B)R^(C)R^(D)Y⁺)X⁻

[0035] wherein Y is N or P, and R^(A)-R^(D) are monovalent hydrocarbonradicals preferably selected from the group consisting of alkyl,alkenyl, aryl, alkaryl, aralkyl, and cycloalkyl moieties or radicals,optionally substituted with suitable heteroatom-containing functionalgroups. The onium salts are generally selected to be less preferentiallyless soluble in the less polar of the two distinct liquid phases. Any ofthe salts disclosed in the U.S. Pat. No. 3,992,432 will be foundeffective, but most preferred are those in which the total number ofcarbon atoms in R^(A),R^(B),R^(C), and R^(D) cumulatively range fromabout 13 to about 57, and preferably range from about 16 to about 30.Most preferred onium salts have Y=N, and hydrocarbon radicals whereR^(A) is CH₃, and R^(B), R^(C), and R^(D) are each selected from thegroup consisting of n-C₂H₅, n-C₄H₅; n-C₅H₁₇; mixed C₅H₁₇; n-C₁₂H₂₅;n-C₁₈H₃₇; mixed C₈-C₁₀ alkyl; and the like. However, R^(A) may also beselected from C₂H₅n-C₃H₇ and n-C₄H₉ benzyl.

[0036] Various counterions may be used, including Cl⁻, Br⁻, I⁻, NO₃ ⁻,SO₄ ⁻², HSO₄ ⁻ and CH₂CO₂ ⁻. Most preferred is Cl⁻.

[0037] The tertiary amines or triamines useful as phase transfercatalysts in this synthesis include the alkyl amines and thearyldialkylamines, exemplified by tributylamine and phenyldibutylaminerespectively, which are commonly available, wherein each alkyl may havefrom 1 to about 16 carbon atoms.

[0038] The polyethers useful as catalysts in this synthesis includecyclic polyethers such as the crown ethers, disclosed in AgenwandteChemie, supra, and acyclic polyethers having the formula:

R—O—R^(E)

[0039] wherein R and R^(E) are, independently, alkyls having from 1 toabout 16 carbon atoms, or alkyl containing substituted functional groupssuch as hydroxy, sulfur, amine, ether, etc. Most preferred acyclicpolyethers have the formula:

R—(OCH₂CH₂)_(r)OR″

[0040] wherein

[0041] R is an alkyl having from 1 to about 16 carbon atoms

[0042] R″ is an alkyl having from 1 to about 16 carbon atoms, or H, and

[0043] r is an integer in the range from 0 to about 300.

[0044] Most preferred are commonly available polyethers such as:tetraethylene glycol dimethyl ether; polyethylene oxide (mol wt. About5000); poly(ethylene glycol methyl ether); 1,2-dimethoxyethane; diethylether, and the like.

[0045] Polyether catalysts are especially desirable in this ketoformsynthesis because they are directive so as to produce a preponderance ofthe desired symmetrically substituted isomer, in a reaction which isremarkably free of undesirable byproducts, which reaction proceeds witha relatively mild exotherm so that the reaction is controllable.

[0046] The organic solvent may be any solvent in which the reactants aresoluble and include hydrohalomethylenes, particularlyhydrochloromethylenes, sulfolane, dibutyl ether, dimethyl sulfone,diisopropyl ether, di-n-propyl ether, 1,4-dioxane, tetrahydrofuran,benzene, toluene, hexane, carbon tetrachloride, heptane, mineral spiritsand the like. Most preferred solvents are heptanes and mineral spirits.Solvent is generally utilized in an amount generally from about 10 toabout 500 percent and preferably from about 50 percent to about 200percent based on the total weight of the reactants.

[0047] Insofar as the reactive components are concerned, any of variousketones having the general formula:

[0048] can be employed in the synthesis, wherein R¹ and R² are describedherein above. As carbon disulfide is the controlling agent in thereaction, the ketone is generally used in an amount from about 110 molepercent to about 2,000 mole percent per mole of carbon disulfide. Whenthe ketone is used as a solvent, it is generally utilized in an amountof from about 150 mole percent to about 300 mole percent, and preferablyfrom about 180 mole percent to about 250 mole percent per mole of carbondisulfide.

[0049] The alkali bases suitable for use in the synthesis of the presentinvention include, but are not limited to, sodium hydroxide andpotassium hydroxide. The base is utilized in an amount generally fromabout 5 times to about 15 times the number of moles of carbon disulfideand preferably from about 6 to about 10 times the number of moles ofcarbon disulfide utilized in the reaction.

[0050] The acids used in the acidification step include, but are notlimited to, hydrochloric acid, sulfuric acid, phosphoric acid, etc. Theacids are utilized in amounts suitable to make the aqueous solutionacidic.

[0051] The haloform of the present invention has the general formulaCHX₃ wherein X is, independently, chlorine or bromine. The amount ofhaloform used in the present invention is generally from about 110 molepercent to about 2000 mole percent, desirably from about 150 molepercent to about 300 mole percent, and preferably 180 mole percent toabout 250 mole percent per mole of carbon disulfide. Examples ofhaloforms include, but are not limited to, chloroform and bromoform, andchloroform is the preferred haloform of the present invention.

[0052] Alternatively, instead of adding both a haloform and a ketone, tothe reaction mixture, an α-trihalomethyl-α-alkanol can be substitutedtherefore. The amount of α-trihalomethyl-α-alkanol utilized in thereaction generally is from about 110 mole percent to about 2000 molepercent, desirably is from about 150 mole percent to about 300 molepercent, and preferably is from about 180 mole percent to about 250 molepercent per mole of carbon disulfide. The general formula of theα-trihalomethyl-α-alkanol is generally represented as follows:

[0053] wherein X, R¹ and R² are defined above.

[0054] While not wishing to be limited to any particular mechanism, itis believed that the specific mechanism for the reaction process is asfollows:

[0055] Initially, the carbon disulfide and sodium hydroxide are reacted.

[0056] In the subsequent step of the reaction, the chloroform is reactedwith the ketone as follows:

[0057] Then, the following is reacted:

[0058] The s,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonatecompounds produced by the present invention can generally be classifiedas inifertors, meaning that they act as both a chain transfer agent andan initiator. The use of other types of inifertors for block copolymerswas discussed by Yagei and Schnabel in Progress in Polymer Science 15,551 (1990) and is hereby fully incorporated by reference.

[0059] Thus, the compounds of the present invention can be utilized asinitiators to initiate or start the polymerization of a monomer. Theycan also act as a chain transfer agent, which interrupts and terminatesthe growth of a polymer chain by formation of a new radical which canact as a nucleus for forming a new polymer chain. The compounds can alsobe utilized as terminators in that when most of initiating radicals andmonomers are consumed, the compounds are incorporated in the polymers asa dormant species. Desirably though, another compound, such as thoselisted herein below, is often used as an initiator in the free radicalpolymerization process as described herein below, and thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundsof the present invention will act as a chain-transfer agent.

[0060] The s,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonatecompounds of the present invention can be used as chain transfer agentsin a free radical polymerization process to provide polymerizationswhich have living characteristics and polymers of controlled molecularweight and low polydispersity, as well as for forming telechelicpolymers.

[0061] A living polymerization is a chain polymerization which proceedsin the absence of termination and chain transfer. The followingexperimental criteria can be utilized to diagnose a livingpolymerization.

[0062] 1. Polymerization proceeds until all monomer has been consumed.Further addition of monomer results in continued polymerization.

[0063] 2. The number average molecular weight, M_(n) (or X_(n), thenumber average degree of polymerization), is a linear function ofconversion.

[0064] 3. The number of polymer molecules (and active centres) isconstant and independent of conversion.

[0065] 4. The molecular weight can be controlled by the stoichiometry ofthe reaction.

[0066] 5. Narrow molecular weight distribution polymers are produced.

[0067] 6. Chain-end functionalized polymers can be prepared inquantitative yields.

[0068] 7. In radical polymerization, the number of active end groupsshould be 2, one for each end.

[0069] Besides those mentioned above, other criteria can also help todetermine the living character of polymerization. For radical livingpolymerization, one is the ability of the polymer isolated from thefirst step of polymerization to be used as a macroinitiator for thesecond step of a polymerization in which block copolymers or graftedpolymers are ultimately formed. To confirm the formation of blockcopolymers, measurements of molecular weights and a determination of thestructure of the blocks are employed. For structure measurements, theexamination of NMR or IR signals for the segments where individualblocks are linked together and a determination of the end groups areboth very important. In radical polymerization, only some of thecriteria for living polymerizations are actually fulfilled. Due to theirability to undergo further polymerization, these types of polymers canalso be called ‘reactive polymers’. A more detailed description ofliving polymerization can be found in “Living Free-Radical BlockCopolymerization Using Thio-Inifertors”, by Anton Sebenik, Progress inPolymer Science, vol. 23, p. 876, 1998.

[0070] The living polymerization processes can be used to producepolymers of narrow molecular weight distribution containing one or moremonomers sequences whose length and composition are controlled by thestoichiometery of the reaction and degree of conversion. Homopolymers,random copolymers or block polymers can be produced with a high degreeof control and with low polydispersity. Low polydispersity polymers arethose with polydispersities that are significantly less than thoseproduced by conventional free radical polymerization. In conventionalfree radical polymerization, polydispersities (polydispersity is definedas the ratio of the weight average to the number average molecularweight M_(w)/M_(n)) of the polymers formed are typically greater than2.0. Polydispersities obtained by utilizing thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundsand derivatives thereof of the present invention are preferably 1.75 or1.5, or less, often 1.3 or less, and, with appropriate choice of thechain transfer agent and the reaction conditions, can be 1.25 or less.

[0071] When the s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonates compounds are utilized only as chain-transferagents, the polymerization can be initiated with other initiators atlower temperature while yielding polymers with similarly controlledfashion.

[0072] Free radical polymerizations utilizing thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundsas both initiators and chain transfer agents generally form telechelicpolymers. When an initiator other than thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundis also utilized, a polymer having a single functional end group isformed in proportion to the amount of said other initiator to thiss,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundutilized.

[0073] The free radical living polymerization process of the inventioncan be applied to any monomers or monomer combinations which can befree-radically polymerized. Such monomers include one or more conjugateddiene monomers or one or more and vinyl containing monomers, orcombinations thereof.

[0074] The diene monomers have a total of from 4 to 12 carbon atoms andexamples include, but are not limited to, 1,3-butadine, isoprene,1,3-pentadiene, 2,3-dimethyl-1-3-butadeine, 2-methyl-1,3-pentadiene,2,3-dimethyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, and4,5-diethyl-1,3-octadiene, and combinations thereof.

[0075] The vinyl containing monomers have the following structure:

[0076] where R³ comprises hydrogen, halogen, C₁ to C₄ alkyl, orsubstituted C₁-C₄ alkyl wherein the substituents, independently,comprise one or more hydroxy, alkoxy, aryloxy(OR⁵), carboxy, metalcarboxylate (COOM) with M being sodium, potassium, calcium, zinc or thelike or an ammonium salt, acyloxy, aroyloxy(O₂CR⁵),alkoxy-carbonyl(CO₂R⁵), or aryloxy-carbonyl; and R⁴ comprises hydrogen,R⁵, CO₂H, CO₂R⁵, COR⁵, CN, CONH₂, CONHR⁵, O₂CR⁵, OR⁵, or halogen. R⁵comprises C₁ to C₁₈ alkyl, substituted C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl,aryl, heterocyclyl, aralkyl, or alkaryl, wherein the substituentsindependently comprise one or more epoxy, hydroxy, alkoxy, acyl,acyloxy, carboxy (and salts), sulfonic acid (and salts), alkoxy- oraryloxy-carbonyl, dicyanato, cyano, silyl, halo and dialkylamino.Optionally, the monomers comprise maleic anhydride, N-vinyl pyrrolidone,N-alkylmaleimide, N-arylmaleimide, dialkyl fumarate andcyclopolymerizable monomers. Monomers CH₂═CR³R⁴ as used herein includeC₁-C₈ acrylates and methacrylates, acrylate and methacrylate esters,acrylic and methacrylic acid, styrene, α methyl styrene, C₁,-C₁₂ alkylstyrenes with substitute groups both either on the chain or on the ring,acrylamide, methacrylamide, N- and N,N-alkylacrylamide andmethacrylonitrile, mixtures of these monomers, and mixtures of thesemonomers with other monomers. As one skilled in the art would recognize,the choice of comonomers is determined by their steric and electronicproperties. The factors which determine copolymerizability of variousmonomers are well documented in the art. For example, see: Greenley, R.Z., in Polymer Handbook, 3^(rd) Edition (Brandup, J., and Immergut, E H.Eds.) Wiley: New York, 1989 pII-53.

[0077] Specific monomers or comonomers include the following: methylmethacrylate, ethyl methacrylate, propyl methacrylate (all isomers),butyl methacrylate (all isomers), 2-ethylhexyl methacrylate, isobornylmethacrylate, methacrylic acid, benzyl methacrylate, phenylmethacrylate, methacrylonitrile, alpha-methylstyrene, methyl acrylate,ethyl acrylate, propyl acrylate (all isomers), butyl acrylate (allisomers), 2-ethylhexyl acrylate, isobornyl acrylate, acrylic acid,benzyl acrylate, phenyl acrylate, acrylonitrile, styrene, functionalmethacrylates, acrylates such as glycidyl methacrylate, 2-hydroxyethylmethacrylate, hydroxypropyl methacrylate (all isomers), hydroxybutylmethacrylate (all isomers), N,N-dimethylaminoethyl methacrylate,N,N-diethylaminoethyl methacrylate, and triethyleneglycol methacrylate,itaconic anhydride, itaconic acid; metal salts such as but not limitedto sodium and zinc of all monomeric acids, such as but not limited to,itaconic acid and 2-acrylamido-2-methyl-1-propanesulfonic acid, or thelike; N-vinylimidazole, vinylpyridine N-oxide, 4-vinylpyridinecarboxymethylbetaine, diallyl dimethylammonium chloride,p-styrenesulfonic acid, p-styrenecarboxylic acid, 2-dimethylaminioethylacrylate and its alkyl/hydrogen halide salts, 2-dimethylaminoethylmethacrylate and its alkyl/hydrogen halide salts,N-(3-dimethylaminopropyl) acrylamide, N-(3-dimethylaminoproyl)methacrylamide, diacetone acrylamide, 2-(acetoacetoxy)ethylmethacrylate, 2-(acryloyloxy)ethyl acetoacetate,3-trialkoxysilylpropylmethacrylate (methoxy, ethoxy, isopropoxy, etc),glycidyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate (allisomers), hydroxybutyl acrylate (all isomers), N,N-diethylaminoethylacrylate, triethyleneglycol acrylate, methacrylamide,N-methylacrylamide, N,N-dimethylacrylamide, N-terbtbutylmethacrylamide,N-n-butylmethacrylamide, N-methylolmethacrylamide,N-ethylotmethacrylamide, N-tert-butylacrylamide, N-N-butylacrylamide,N-methylolacrylamide, N-ethylolacrylamide, vinyl benzoic acid (allisomers), dethylaminostyrene (all isomers), alpha-methylvinyl benzoicacid (all isomers), dethylamino alpha-methylstyrene (all isomers),p-vinylbenzene sulfonic acid, p-vinylbenzene sulfonic sodium salt,trimethoxysilyipropyl methacrylate, triethoxysilylpropyl methacrylate,tributoxysilyipropyl methacrylate, dimethoxymethylsilylpropylmethacrylate, diethoxymethylslylpropyl methacrylate,dibutoxymethylsilypropyl methacrylate, diisopropoxymethylsilylpropylmethacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropylmethacrylate, dibutoxy, silylpropyl methacrylate,diisopropoxysilyipropyl methacrylate, trimethoxysilylpropyl acrylate,triethoxysifylylpropyl acrylate, tributoxysilylpropyl acrylate,dimethoxymethylsilylpropyl acrylate, diethoxymethylsilylpropyl acrylate,dibutoxymethylsilylpropyl acrylate, diisopropoxymethylsilylpropylacrylate, dimethoxysilylpropyl acrylate, diethoxysilylpropyl acrylate,dibutoxysilyipropyl acrylate, diisopropoxysilylpropyl amiate, vinylacetate, vinyl butyrate, vinyl benzoate, vinyl chloride, vinyl fluoride,vinyl bromide, maleic anhydride, N-phenylmaleimide, N-butylmaleimide,N-vinylpyrrolidone, N-vinylcarbazole, butadiene, isoprene, chloroprene,ethylene, and propylene, and combinations thereof.

[0078] Preferred monomers are C₁-C₁₈ acrylates; C₁-C₈ monoalkyl anddialkyl acrylamides; a combination of C₁-C₈ acrylates and methacrylates;a combination of acrylamides and methacrylamide; C₁-C₈ styrene;butadiene; isoprene and acrylonitrile.

[0079] As noted above, in order to initiate the free radicalpolymerization process, it is often desirable to utilize an initiator asa source for initiating free radicals. Generally, the source ofinitiating radicals can be any suitable method of generating freeradicals such as the thermally induced homolytic scission of a suitablecompound(s) (thermal initiators such as peroxides, peroxyesters, or azocompounds), the spontaneous generation from monomer (e.g., styrene),redox initiating systems, photochemical initiating systems or highenergy radiation such as electron beam, X- or gamma-radiation. Theinitiating system is chosen such that under the reaction conditionsthere is no substantial adverse interaction of the initiator or theinitiating radicals with the transfer agent under the conditions of theexperiment. The initiator should also have the requisite solubility inthe reaction medium or monomer mixture. Thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundsof the invention can serve as an initiator, but the reaction must be runat a higher temperature. Therefore, optionally it is desirable toutilize an initiator other than thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonates compoundsof the present invention.

[0080] Thermal initiators are chosen to have an appropriate half-life atthe temperature of polymerization. These initiators can include one ormore of the following compounds:

[0081] 2,2′-azobis(isobutyronitrile)(AIBN),2,2′-azobis(2-cyano-2-butane), dimethyl 2,2′-azobisdimethylisobutyrate,4,4′-azobis(4-cyanopentanoic acid),1,1′-azobis(cyclohexanecarbanitrile), 2-(t-butylazo)-2-cyanopropane,2,2′-azobis[2-methyl-N-(1,1)-bis(hydoxymethyl)-2-hydroxyethyl]propionamide, 2,2′-azobis[2-methyl-N-hydroxyethyl)]-propionamide,2,2′-azobis(N,N′-dimethyleneisobutyramidine) dihydrochloride,2,2′-azobis(2-amidinopropane) dihydrochloride,2,2′-azobis(N,N′-dimethyleneisobutyramine),2,2′-azobis(2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide), 2,2′-azobis(2-methyl-N-[1,1-bis(hydroxymethyl) ethyl]propionamide), 2,2′-azobis[2-methyl-N-(2-hydroxyethyl) propionamide],2,2′-azobis(isobutyramide) dehydrate,2,2′-azobis(2,2,4-trimethylpentane), 2,2′-azobis(2-methylpropane),t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl peroxyoctoate,t-butylperoxyneodecanoate, t-butylperoxy isobutyrate, t-amylperoxypivalate, t-butyl peroxypivalate, di-isopropyl peroxydicarbonate,dicyclohexyl peroxydicarbonate, dicumyl peroxide, dibenzoyl peroxide,dilauroylperoxide, potassium peroxydisulfate, ammonium peroxydisulfate,di-t-butyl hyponitrite, dicumyl hyponitrite.

[0082] Photochemical initiator systems are chosen to have the requisitesolubility in the reaction medium or monomer mixture and have anappropriate quantum yield for radical production under the conditions ofthe polymerization. Examples include benzoin derivatives, benzophenone,acyl phosphine oxides, and photo-redox systems production under theconditions of the polymerization; these initiating systems can includecombinations of the following oxidants and reductants:

[0083] oxidants: potassium peroxydisuffate, hydrogen peroxide, t-butylhydroperoxide reductants: iron (11), titanium (111), potassiumthiosulfite, potassium bisulfite.

[0084] Other suitable initiating systems are described in recent texts.See, for example, Moad and Solomon “The Chemistry of Free RadicalPolymerization”. Pergamon, London. 1995. pp 53-95.

[0085] The preferred initiators of the present invention are2,2′-azobis(isobutyronitrile)(AIBN), or 4,4′-azobis(4-cyanopentanoicacid), or 2,2′-azobis(2-cyano-2-butane), or1,1′-azobis(cyclohexanecarbanitrile). The amount of initiators utilizedin the polymerization process can vary widely as generally from about0.001 percent to about 99 percent, and desirably from about 0.01 percentto about 50 or 75 percent based on the total moles of chain transferagent utilized. Preferably small amounts are utilized from about 0.1percent to about 5, 10, 15, 20, or 25 mole percent based on the totalmoles of chain transfer agent utilized, i.e. saids,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compounds.In order to form polymers which are predominately telechelic, initiatorsother than the s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate compounds are utilized in lesser amounts, such asfrom about 0.001 percent to about 5 percent, desirably from about 0.01percent to about 4.5 percent, and preferably from about 0.1 percent toabout 3 percent based on the molar equivalent to the total moles ofchain transfer agent utilized.

[0086] Optionally, as noted above, solvents may be utilized in the freeradical polymerization process. Examples of such solvents include, butare not limited to, C₆-C₁₂ alkanes, toluene, chlorobenzene, acetone,t-butyl alcohol, and dimethylformamide. The solvents are chosen so thatthey do not chain transfer themselves. The amount of solvent utilized inthe present invention polymerization process is generally from about 10percent to about 500 percent the weight of the monomer, and preferablyfrom about 50 percent to about 200 percent the weight of the monomerutilized in the polymerization.

[0087] As stated above, it is preferable to utilize thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundsof the invention as chain transfer agents in the free radicalpolymerization process. The amount of chain transfer agent (CTA)utilized depends on the desired molecular weight of the polymer to beformed and can be calculated as known by one skilled in the art. Aformula for calculating the amount of chain transfer agent is asfollows: $\begin{matrix}\begin{matrix}{\begin{matrix}{{Mn}\quad {of}} \\{polymer}\end{matrix} = {( \frac{{Weight}\quad {of}\quad {monomer} \times {molecular}\quad {weight}\quad {CTA}}{{Weight}\quad {of}\quad {CTA}} ) +}} \\{{{molecular}\quad {weight}\quad {of}\quad {CTA}}}\end{matrix} & {{XII}\quad (a)}\end{matrix}$

[0088] While not wishing to be limited to any particular mechanism, itis believed that the mechanism of the free radical living polymerizationprocess is as follows when using a vinyl monomer:

[0089] Alternatively, the reaction can proceed as follows:

[0090] As can be seen from the above mechanism, polymers having twodifferent structures, see XIX and XXII, can be formed. The resultingpolymers are either telechelic polymers (formed by the trithiocarbonatecompounds of the present invention) with identical functional groups atthe ends of the chain, or a polymer having a single functional end groupand also an initiator terminated chain (formed by using a conventionalinitiator such as AIBN). As stated above, the ratios between theresulting polymers can be controlled to give desired results andgenerally depends on the amount of initiator utilized. Obviously, if theinitiator is the only s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate compound of the present invention, the resultingpolymers are always telechelic. The greater the amount of the otherinitiator utilized, proportionally decreases the amount of telechelicpolymers formed. Generally, the amount of the repeat group m, m′, m″, n,n′, or n″, is generally from about 1 to about 10,000, desirably fromabout 5 to about 500, and preferably from about 10 to about 200.Inasmuch as one or more vinyl monomers and/or one or more diene monomerscan be utilized, it is to be understood that repeat groups of thepolymers of the present invention are generally indicated by formulasXIX and XXII and can be the same or different. That is, randomcopolymers, terpolymers, etc., can be formed within either of the tworepeat groups noted, as well as block copolymers which can be formed byinitially adding one monomer and then subsequently adding a differentmonomer (e.g. an internal block copolymer).

[0091] The polymers formed by the present invention can be generallyrepresented by the following formula:

[0092] wherein such monomers are described herein above. Of course, theabove formula can contain an initiator end group thereon as in XXII.

[0093] The reaction conditions are chosen as known to one skilled in theart so that the temperature utilized will generate a radical in acontrolled fashion, wherein the temperature is generally from about roomtemperature to about 200° C. The reaction can be run at temperatureslower than room temperature, but it is impractical to do so. Thetemperature often depends on the initiator chosen for the reaction, forexample, when AIBN is utilized, the temperature generally is from about40° C. to about 80° C., when azo dicyanodivaleric acid is utilized, thetemperature generally is from about 50° C. to about 90° C., whendi-t-butylperoxide is utilized, the temperature generally is from about110° C. to about 160° C., when s,s′-bis-(α,α′-disubstituted-α″-aceticacid) is utilized, the temperature is generally from about 80° C. toabout 200° C.

[0094] The low polydispersity polymers prepared as stated above by thefree radical polymerization can contain reactive end groups from themonomers which are able to undergo further chemical transformation orreaction such as being joined with another polymer chain, such as toform block copolymers for example. Therefore, any of the above listedmonomers, i.e. conjugated dienes or vinyl containing monomers, can beutilized to form block copolymers utilizing thes,s′-bis-(α,α′-distributed-α″-acetic acid)-trithiocarbonate compounds aschain transfer agent. Alternatively, the substituents may benon-reactive such as alkoxy, alkyl, or aryl. Reactive groups should bechosen such that there is no adverse reaction with the chain transferagents under the conditions of the experiment.

[0095] The process of this invention can be carried out in emulsion,solution or suspension in either a batch, semi-batch, continuous, orfeed mode. Otherwise-conventional procedures can be used to producenarrow polydispersity polymers. For lowest polydispersity polymers, thechain transfer agent is added before polymerization is commenced. Forexample, when carried out in batch mode in solution, the reactor istypically charged with chain transfer agent and monomer or medium plusmonomer. The desired amount of initiator is then added to the mixtureand the mixture is heated for a time which is dictated by the desiredconversion and molecular weight. Polymers with broad, yet controlled,polydispersity or with multimodal molecular weight distribution can beproduced by controlled addition of the chain transfer agent over thecourse of the polymerization process.

[0096] In the case of emulsion or suspension polymerization the mediumwill often be predominately water and the conventional stabilizers,dispersants and other additives can be present. For solutionpolymerization, the reaction medium can be chosen from a wide range ofmedia to suit the monomer(s) being used.

[0097] As already stated, the use of feed polymerization conditionsallows the use of chain transfer agents with lower transfer constantsand allows the synthesis of block polymers that are not readily achievedusing batch polymerization processes. If the polymerization is carriedout as a feed system the reaction can be carried out as follows. Thereactor is charged with the chosen medium, the chain transfer agent andoptionally a portion of the monomer(s). The remaining monomer(s) isplaced into a separate vessel. Initiator is dissolved or suspended inthe reaction medium in another separate vessel. The medium in thereactor is heated and stirred while the monomer+medium andinitiator+medium are introduced over time, for example by a syringe pumpor other pumping device. The rate and duration of feed is determinedlargely by the quantity of solution the desired monomer/chain transferagent/initiator ratio and the rate of the polymerization. When the feedis complete, heating can be continued for an additional period.

[0098] Following completion of the polymerization, the polymer can beisolated by stripping off the medium and unreacted monomer(s) or byprecipitation with a non-solvent. Alternatively, the polymersolution/emulsion can be used as such, if appropriate to itsapplication.

[0099] The invention has wide applicability in the field of free radicalpolymerization and can be used to produce polymers and compositions forcoatings, including clear coats and base coat finishes for paints forautomobiles and other vehicles or industrial, architectural ormaintenance finishes for a wide variety of substrates. Such coatings canfurther include pigments, durability agents, corrosion and oxidationinhibitors, rheology control agents, metallic flakes and otheradditives. Block and star, and branched polymers can be used ascompatibilizers, thermoplastic elastomers, dispersing agents or rheologycontrol agents. Additional applications for polymers of the inventionare in the fields of imaging, electronics (e.g., photoresists),engineering plastics, adhesives, sealants, paper coatings andtreatments, textile coatings and treatments, inks and overprintvarnishes, and polymers in general.

[0100] As can be seen in the above shown polymerization mechanism, thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundcan be utilized to create telechelic polymers having two functionalgroups at both chain ends.

[0101] The term “telechelic polymer” was proposed in 1960 by Uraneck etal. to designate relatively low molecular weight macromoleculespossessing one or more, and preferably two reactive functional groups,situated at the chain ends, thereof. The functional end groups of boththe s,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonatecompound and the polymers formed therefrom, have the capacity forselective reaction to form bonds with another molecule. Thefunctionality of a telechelic polymer or prepolymer is equal to thenumber of such end groups. Telechelic polymers containing a functionalgroup, such as COOH, at each end are useful for synthesizing furtherchain extended copolymers and block copolymers.

[0102] The interest in telechelic polymers resides in the fact that suchpolymers can be used, generally together with suitable linking agents,to carry out three important operations: (1) chain extension of shortchains to long ones by means of bifunctional linking agents, (2)formation of networks by use of multifunctional linking agents, and (3)formation of (poly)block copolymers by combination of telechelics withdifferent backbones. These concepts are of great industrial importancesince they form the basis of the so-called “liquid polymer” technologyexemplified by the “reaction injection molding” (RIM). Great interesthas also been shown by the rubber industry because the formation of arubber is based on network formation. In classical rubber technology,this is achieved by the cross-linking of long chains that show highviscosity. The classical rubber technology, therefore, requires anenergy-intensive mixing operation. The use of liquid precursors, whichcan be end-linked to the desired network, offers not only processingadvantages, but in some cases, also better properties of theend-product. Further information about telechelic polymers and synthesisthereof can be found in “Telechelic Polymers: Synthesis andApplications” by Eric J. Goethe, CRC Press, Boca Raton, Fla., 1989.

[0103] The reaction conditions for the reactive functional acid endgroups of the telechelic polymers ors,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundsof the present invention are generally the same as those for forming theabove noted free radical polymers. The acid in the monomeric or in thepolymeric form can be transformed to its derivatives in the conventionalmanner. For example, the ester can be made by refluxing the acid inalcohol with an acid catalyst with removal of water. Amides can beformed by heating the acid with an amine with the removal of water.2-hydroxy-ethyl ester can be formed by directly reacting the acid withan epoxide with or without a catalyst such as triphenylphosphine or anacid like toluene-sulfonic acid. As seen by the examples below, any ofthe above noted monomers such as the one or more diene monomers or oneor more vinyl containing monomers, can be utilized to form thetelechelic monomers from the bis-(α,α′-distributed-α″-aceticacid)-trithiocarbonate compounds of the present invention. Any of theabove noted components, such as solvent, etc., can be utilized in theherein above stated amounts.

[0104] The acid groups of the s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate compound can be converted to other functionalgroups either before or after polymerization. Even if thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundshave functional end groups which have been converted from the acid endgroups before polymerization, the monomers added during polymerizationstill add to the chain between the sulfur-tertiary carbon as shown inthe mechanisms above as well as below at XXIII and XXIV. The carboxylicend groups of the s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate compounds or the polymerizeds,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundscan be converted or changed into other functional end groups such asesters, thioesters, amides, beta mercapto esters, beta hydroxy esters,or beta amino esters. Examples of these functional end groups are shownbelow.

[0105] An example reaction forming a telechelic polymer from thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundsof the invention when using a vinyl monomer is as follows:

[0106] Of course, it is to be understood as indicated above, that therepeat units m and n can be derived either from conjugated dienemonomers, or the indicated vinyl monomers, or combinations thereof, asgenerally set forth in formula W.

[0107] Subsequently, other functional end groups can be derived from theacid groups of the s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate compound and can generally be represented by theformula:

[0108] wherein E is XR′, that is R′, independently, comprises H, C₁-C₁₈alkyls which can be optionally substituted with one or more halogen,hydroxyl, or alkoxy, C₁-C₁₈ hydroxyalkyls, and C₁-C₁₈ aminoalkyls and Xcomprises oxygen, sulfur, NH, or NR′.

[0109] The following is still another example of functional end groupswhich can be derived from the acid:

[0110] that is where R⁶ through R⁹, independently comprise H, C₁-C₁₈alkyls, aryl groups or substituted aryl groups having from 1 to 6substituents on the ring, such as halogen, hydroxyl, or alkoxy, C₁-C₁₈hydroxyalkys, C₁-C₁₈ aminoalkyls, C₁-C₁₈ mercapto alkyls, and the like.Y can comprise oxygen, sulfur, NH, or NR⁶ to R⁹.

[0111] A further example of still other functional end groups which canbe derived from the acid groups of thes,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate compoundsis as follows:

[0112] wherein E is OR¹⁰, that is where Z can comprise a leaving group,such as a halide or alkylsulfonate or aryl sulfonate. R¹⁰ can compriseC₁-C₁₈, a alkyl or substituted alkyl wherein said substituent ishalogen, hydroxyl, or alkoxy, C₁-C₁₈ hydroxyalkyl or C₁-C₁₈ amino alkyland the like.

[0113] Preparation of the above shown methylesters ofs,s′-bis-(2-methyl-2-propanoic acid)-trithiocarbonate is as follows:s,s′-bis-(2-methyl-2-propanoic acid) trithiocarbonate (R¹,R²=CH³) (2.82g, 0.01 mole), Sodium carbonate powders (3.18 g, 0.03 mole) and 15 mldimethyl formamide were stirred under nitrogen at 40° C. while asolution of methyliodide (3.41 g, 0.024 mole) in 2 ml dimethylformamidewas added dropwise over 10 minutes. The reaction was stirred at 40-50°C. f or 2 hours, poured into 25 ml H₂O and extracted 3 times with atotal of 200 ml. ether. The etherate solution was dried over magnesiumsulfate and concentrated. The yellow solid was further purified byrecrystallization from hexanes. Infrared and H′NMR showed the abovedesired product.

[0114] An example of an already formed telechelic polymer, made from avinyl monomer, undergoing conversion of the acid end group is asfollows:

[0115] where m and n are as set forth above.

[0116] The above structure (XXXIV) was formed by reaction of epoxidewith s,s′-bis-(2-methyl-2-propanoic acid)-trithiocarbonate(I)(R¹,R²=CH₃, 0.01 mole) of the present invention and Epon® Resin 828(Resolution Performance Products, reaction product of bisphenol A andepichlorohydrin, 80-85% diglycidyl ethers of bisphenol A) (70 g) andtrephenyl phosphine (0.12 g) were heated to 95° C. under nitrogen. Thereaction was monitored for the disappearance of the carboxylic acid bytitration. It was found the reaction was essentially complete in 1.5hours. The product structure can be further confirmed by massspectroscopy.

[0117] Another aspect of present invention further relates to formingthe following compounds:

[0118] wherein R¹¹ comprises a benzyl group, C₁-C₁₈ alkyl, orsubstituted alkyl such as halogen, hydroxyl, or alkoxy, C₁-C₁₈hydroxyalkyl, carboxylalkyl, or carboalkoxyalkyl. Q⁺X is a phasetransfer catalyst such as tetrabutylammoniumhydrogensulfate, oroctadecyltrimethylammoniumchloride (Aliquot 336).

[0119] The resulting compound is an s-substitutedalkyl-s′-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonate. R¹¹ is analkyl having from 1-18 carbon atoms, aralkyl, hydroxyalkyl, cyanoalkyl,aminoalkyl, carboxylalkyl, or carboalkoxyalkyl, mercaptoalkyl, etc. R¹and R² are as stated herein above.

[0120] When s-substituted alkyl-s′-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate is employed either as an inifertor, or as achain-transfer agent, unless R¹¹ is carboxyl alkyl, only one end of thepolymer has a carboxyl function, i.e. it is no longer a telechelicpolymer.

[0121] While various polymers have been set forth herein above, it is tobe understood that any of the carboxyl terminated polymers, such as W,or the E terminated polymers, and the like, can be reacted with one ormore monomers and/or one or more polymers know to the art and to theliterature to yield various resulting block polymers which are derivedfrom the same monomer or from two or more different monomers. Forexample, each acid end group can be reacted with an excess of an epoxycompound such as a glycidyl bisphenol A and then subsequentlypolymerized with additional glycidyl bisphenol A to form an epoxypolymer. Naturally, other block polymers or copolymers can be reactedwith the carboxylic end group or the other end groups generally denotedby E hereinabove.

Dithiocarbonates I. Dithiocarbamates

[0122] A further embodiment of the present invention relates todithiocarbonate compounds which have the general formula:

[0123] wherein j is 1 or 2, with the proviso that when j is 1, T isNR¹⁵R¹⁶); and when j is 2, T is a divalent radical having a nitrogenatom directly connected to each carbon atom of the two thiocarbonylgroups present;

[0124] wherein R¹² and R¹³, independently, is the same or different, isoptionally substituted, and is a linear or branched alkyl having from 1to about 6 or about 12 carbon atoms; or an aryl group having from 6 toabout 18 carbon atoms, optionally containing heteroatoms;

[0125] wherein the R¹² and/or R¹³ substituents, independently, comprisean alkyl having from 1 to 6 carbon atoms; an aryl group; a halogen; acyano group; an ether having a total of from 2 to about 20 carbon atoms;a nitro; or combinations thereof. R¹² and R¹³ can also form or be a partof a substituted or unsubstituted cyclic ring having from 3 to about 12total carbon atoms wherein the substituents are described above. R¹² andR¹³ are preferably, independently, methyl or phenyl groups;

[0126] wherein R¹⁵ and R¹⁶, independently, is the same or different,optionally is substituted, optionally contains heteroatoms; and ishydrogen; a linear or branched alkyl having from 1 to about 18 carbonatoms, an aryl group having from about 6 to about 18 carbon atomsoptionally saturated or unsaturated; an arylalkyl having from about 7 toabout 18 carbon atoms; an alkenealkyl having from 3 to about 18 carbonatoms; or derived from a polyalkylene glycol ether having from 3 toabout 200 carbon atoms. R¹⁵ and R¹⁶ can also be derived from amines suchas, but not limited to, piperazine, morpholine, pyrrolidine, piperidine,4-alkyl amino-2,2,6,6-tetramethyl piperidine,1-alkylamioalkyl-3,3,5,5-tetramethyl-2-piperazinone, hexamethyleneimine,phenothiazine, iminodibenzyl, phenoxazine,N,N′-diphenyl-1,4-phenylenediamine, dicyclohexylamine and derivativesthereof. R¹⁵ and R¹⁶ can also form a substituted or unsubstituted cyclicring, optionally containing heteroatoms, along with the nitrogen havinga total of from 4 to about 12 carbon atoms, such as benzotriazole,tolyltriazole, imidazole, 2-oxazolidone, 4,4-dimethyloxazolidone and thelike. The R¹⁵ and R¹⁶ substituents, independently, can be the same asdescribed herein with respect to R¹⁴. R¹⁵ and R¹⁶ are preferably,independently, a phenyl group or an alkyl or substituted alkyl havingfrom 1 to about 18 carbon atoms such as a methyl group, or R¹⁵ and R¹⁶,independently, are hexamethylene.

[0127] It is to be understood throughout the application formulas,reaction schemes, mechanisms, etc., and the specification that metalssuch as sodium or bases such as sodium hydroxide are referred to and theapplication of the present invention is not meant to be solely limitedthereto. Other metals or bases such as, but not limited to, potassiumand potassium hydroxide, respectively, are contemplated by thedisclosure of the present invention.

[0128] When j is 1, T of above formula is (NR¹⁵R¹⁶ and thedithiocarbamate compound is a S-(α,α′-disubstituted-α″-acetic acid)dithiocarbamate generally having the following formula:

[0129] wherein R¹² R¹³, R¹⁵, and R¹⁶ are as defined hereinabove.

[0130] When j is 2, the dithiocarbarbamate compound is abis-S-(α,α′-disubstituted-α″-acetic acid) dithiocarbamate having thefollowing formula:

[0131] wherein R¹² and R¹³ are defined hereinabove; and

[0132] wherein T is a divalent bridging radical having a nitrogen atomdirectly connected to each of the thiocarbonyl groups present.

[0133] In one embodiment T is:

[0134] wherein R¹⁷ and R¹⁸, independently, is the same or different, isoptionally substituted, and is hydrogen, a linear or branched alkylhaving from 1 to about 18 carbon atoms, an aryl group having from about6 to about 18 carbon atoms, an arylalkyl having from 7 to about 18carbon atoms, an alkenealkyl having from 3 to about 18 carbon atoms,wherein the substitutents can be the same as described herein for R¹ andR²; wherein R¹⁹ is optionally substituted, and is non-existent, or analkylene group having from 1 to about 18 carbon atoms with about 1 toabout 6 carbon atoms preferred, or derived from a polyalkylene glycolether having from 3 to about 200 carbon atoms, wherein the substituentscan be the same as described herein for R¹ and R² or are heteroatomssuch as oxygen, nitrogen, sulfur or phosphorous; and

[0135] wherein R²⁰ and R²¹ independently, is the same or different, andis optionally substituted as described for R¹ and R², and is an alkylenegroup having from 1 to about 4 carbon atoms, with R²⁰ and R²¹ preferablyhaving a collective total of 3 to 5 carbon atoms.

[0136] In further embodiments, T is:

[0137] wherein n is 0 to about 18, with 0 to about 6 preferred;

[0138] wherein n is 0 to about 18, with 0 to about 6 preferred;

[0139] Some specific non-limiting examples of T bridging radicals are:

[0140] The S-(α,α′-disubstituted-α″-acetic acid) or bisS-(α,α′-disubstituted-α″-acetic acid) dithiocarbamates are generally areaction product of a metal salt of a dithiocarbamate, a haloform, and aketone. A phase transfer catalyst, solvent, and a base such as sodiumhydroxide or potassium hydroxide can also be utilized to form theS-(α,α′-disubstituted-α″-acetic acid) or bisS-(α,α′-disubstituted-α″-acetic acid) dithiocarbamates.

[0141] The metal salt of a dithiocarbamate is either prepared orpurchased from a supplier such as Aldrich of Milwaukee, Wis. or Acros ofSommerville, N.J. Metal salts of dithiocarbamates are made in situ fromamine, carbon disulfide, and a metal hydroxide as disclosed in theliterature. Examples of metal salts of dithiocarbamates include sodiumN,N-dimethyl dithiocarbamate and sodium N,N-diethyl-dithiocarbamate.

[0142] The S-(α,α′-disubstituted-α″-acetic acid) or bisS-(α,α′-disubstituted-α″-acetic acid) dithiocarbamate is formed bycombining a metal salt of the dithiocarbamate with a haloform, a ketone,a base, optionally a solvent and a catalyst, in a reaction vesselpreferably under an inert atmosphere. The base is preferably added tothe other components over a period of time to maintain a preferredtemperature range and avoid by-products. The reaction product issubsequently acidified, completing the reaction. The reaction product isisolated as a solid or liquid and is optionally purified.

[0143] The limiting agents of the reaction are usually the amine andcarbon disulfide, or the metal salt of the dithiocarbamate whenutilized. The haloform is utilized in the reaction in an amount fromabout 0 percent to about 500 percent molar excess, with about 50 percentto about 200 percent molar excess preferred. The ketone is utilized inthe reaction in an amount from 0 percent to about 3000 percent molarexcess, with about 100 percent to about 1000 percent molar excesspreferred. The metal hydroxide when utilized, is present in an amountfrom 10 percent to 500 percent molar excess, with about 60 percent to150 percent molar excess preferred.

[0144] The abbreviated reaction formula for theS-(α,α′-disubstituted-α″-acetic acid) dithiocarbamate of the presentinvention is generally as follows:

[0145] The abbreviated reaction formula for the bisS-(α,α′-disubstituted-α″-acetic acid) dithiocarbamate of the presentinvention is generally as follows:

[0146] The reaction is carried out at a temperature sufficient toinitiate and complete reaction of the reactants in order to produce theS-(α,α′-disubstituted-α″-acetic acid) or bisS-(α,α′-disubstituted-α″-acetic acid) dithiocarbamate compound in adesired time. The reaction can be carried out at any temperature withina wide range of from about the freezing point of the reaction mass toabout the reflux temperature of the solvent. The reaction temperature isgenerally from about minus 15° C. to about 80° C., desirably from about0° C. to about 50° C., and preferably from about 15° C. to about 35° C.,with about 15° C. to about 25° C. being preferred. The reaction can beperformed at atmospheric pressure. The reaction time depends on severalfactors, with the temperature being most influential. The reaction isgenerally complete within 20 hours and preferably within about 10 hours.

[0147] A catalyst, preferably a phase transfer catalyst, is generallyutilized when the optional solvent is used in the reaction. Examples ofpreferable catalysts and solvents are listed hereinabove andincorporated by reference. Preferred phase transfer catalysts includetricaprylmethylammonium chloride (Aliquot 336), benzyltriethylammoniumchloride, and tetrabutylammonium hydrogen sulfate. The amount ofcatalyst and solvents utilized in the reaction to form theS-(α,α′-disubstituted-(α″-acetic acid) or bisS-(α,α′-disubstituted-α″-acetic acid) dithiocarbamate compound aregenerally the same as set forth above and herein incorporated byreference. When the ketone is also the solvent, the catalyst isoptionally eliminated from the process.

[0148] The ketones, haloforms, bases, and acids utilized in thedithiocarbamate reaction can be the same as those listed above for thetrithiocarbonate synthesis and amounts thereof are herein incorporatedby reference. Alternatively, an α-trihalomethyl-α-alkanol can beutilized in place of the haloform and ketone in the amounts notedhereinabove for the trithiocarbonate synthesis.

[0149] It is believed that the reaction scheme for the formation of theS-(α,α′-disubstituted-α″-acetic acid) dithiocarbamate is as follows:

[0150] wherein R¹⁵ and R¹⁶ are defined hereinabove. The reaction schemefor the formation of the bis S-(α,α′-disubstituted-α″-acetic acid)dithiocarbonate is similar to the above reaction scheme and obvious toone of ordinary skill in the art. A phase transfer catalyst such astetrabutylammoniumhydrogensulfate or octadecyltrimethylammoniumchloride(Aliquot 336) as mentioned above is utilized in a preferred embodiment.

[0151] The S-(α,α′-disubstituted-α″-acetic acid) or bisS-(α,α′-disubstituted-α″-acetic acid) dithiocarbamate compounds areutilized in essentially the same manner as the trithiocarbonatecompounds mentioned hereinabove. That is, theS-(α,α′-disubstituted-α″-acetic acid) or bisS-(α,α′-disubstituted-α″-acetic acid) dithiocarbamate compounds invarious embodiments are utilized as initiators to initiate or start thepolymerization of a monomer, as a chain transfer agent which interruptsand terminates the growth of a polymer chain by formation of a newradical which can act as the nucleus for forming a new polymer chain,and/or as a terminator which are incorporated into a polymer as adormant species. Preferably, the S-(α,α′-disubstituted-α″-acetic acid)or bis S-(α,α′-disubstituted-α″-acetic acid) dithiocarbamate compoundsare utilized as chain transfer agents in free radical polymerizationshaving living characteristics to provide polymers of controlledmolecular weight and low polydispersity.

Dithiocarbamate (Co)Polymers

[0152] To this end, the present invention also relates to both a processfor forming polymers or copolymer derived from the dithiocarbamatecompounds having the following general formulae:

[0153] wherein R¹², R¹³, R¹⁵, R¹⁶ and T are defined hereinabove, whereinthe polymer is derived from a monomer as described herein, such as butnot limited to, a conjugated diene monomer, or a vinyl containingmonomer, or combinations thereof, wherein each polymer repeat unit isthe same or different, and wherein f is generally from 1 to about10,000, and preferably from about 3 to about 5,000. Preferred polymersare derived from alkyl acrylate, vinyl acetate, acrylic acid, andstyrene. Of course, it is to be understood that when f is 1, the polymeris a single reacted monomer unit.

[0154] The above dithiocarbamate polymers or copolymers can be preparedby bringing into contact with each other the monomer(s) which form(s)the (polymer) repeat units and the S-(α,α′-disubstituted-α″-acetic acid)or bis S-(α,α′-disubstituted-α″-acetic acid) dithiocarbamate compounds,and optionally, a) solvent and b) a radical polymerization initiator; insuitable amounts, as described herein.

[0155] It is believed the polymer forming mechanism for theS-(α,α′-disubstituted-α″-acetic acid) dithiocarbonate compound is asfollows:

[0156] The mechanism for the bis S-(α,α′-disubstituted-α″-acetic acid)dithiocarbonate compound is similar to the above-noted mechanism andobvious to one of ordinary skill in the art.

[0157] As illustrated by the above reaction formulas, the monomers arepolymerized into the dithiocarbamate compounds adjacent to thethiocarbonylthio linkage, between the single bonded sulfur atom and thetertiary carbon atom of the compound.

[0158] The dithiocarbamate compounds of the present invention are usedto produce polymers which are substantially colorless. The polymers orcopolymers of the dithiocarbamate compounds are hydrolytically stablebecause the electro-donating amino groups render the thiocarbonyl groupless electrophilic. The polymers are also stable toward nucleophilessuch as amines.

[0159] The reaction conditions are chosen as known to one ordinarilyskilled in the art so that the temperature utilized will generate aradical in a controlled fashion with the temperature being generallyfrom about room temperature to about 200° C. The reaction can beperformed at temperatures lower than room temperature, but it isimpractical to do so. The temperature often depends on the initiatorchosen for the reaction, for example, when AIBN is utilized, thetemperature generally is from about 40° C. to about 80° C., whenazodicyanodivaleric acid is utilized, the temperature generally is fromabout 50° C. to about 90° C., when di-t-butylperoxide is utilized, thetemperature generally is from about 110° C. to about 160° C., and whenS-(α,α′-disubstituted-α″-acetic acid) or bisS-(α,α′-disubstituted-α″-acetic acid) dithiocarbamate is utilized, thetemperature is generally from about 120° C. to about 200° C.

[0160] The low polydispersity polymers prepared as stated above by thefree radical polymerization can contain reactive end groups from themonomers which are able to undergo further chemical transformation orreaction such as being joined with another polymer chain, such as toform copolymers for example. Therefore, any of the above listedmonomers, i.e. conjugated dienes or vinyl containing monomers, areutilized to form copolymers utilizing theS-(α,α′-disubstituted-α″-acetic acid) or bisS-(α,α′-disubstituted-α″-acetic acid) dithiocarbamate compounds as chaintransfer agent. Moreover, in one embodiment the polymers are crosslinkedusing a crosslinker during polymerization. Suitable crosslinkersinclude, but are not limited to, polyallyl pentaerythritol, polyallylsucrose, trimethylol propane diacrylate, trimethylol propanetriacrylate, glycerol triacrylate, methylene bisacrylamide andethylene-glycol diacrylate. Alternatively, the substituents may benon-reactive such as alkoxy, alkyl, or aryl. Reactive groups should bechosen such that there is no adverse reaction with the chain transferagents under the conditions of the experiment.

[0161] The process of this invention is carried out in emulsion,solution or suspension in either a batch, semi-batch, continuous, orfeed mode. Bulk polymerization (no solvent) is also achieved becausepropagation is slower. Otherwise-conventional procedures can be used toproduce narrow polydispersity polymers. For lowest polydispersitypolymers, the chain transfer agent is added before polymerization iscommenced. The polydispersity of polymers or copolymers produced fromthe dithiocarbamates is generally less than about 3.0. For example, whencarried out in batch mode in solution, the reactor is typically chargedwith chain transfer agent and monomer or medium plus monomer. Thedesired amount of initiator is then added to the mixture and the mixtureis heated for a time which is dictated by the desired conversion andmolecular weight. Polymers with broad, yet controlled, polydispersity orwith multimodal molecular weight distribution can be produced bycontrolled addition of the chain transfer agent over the course of thepolymerization process.

[0162] In the case of emulsion or suspension polymerization the mediumwill often be predominately water and the conventional stabilizers,dispersants and other additives can be present. For solutionpolymerization, the reaction medium can be chosen from a wide range ofmedia to suit the monomer(s) being used.

[0163] As already stated, the use of feed polymerization conditionsallows the use of chain transfer agents with lower transfer constantsand allows the synthesis of block polymers that are not readily achievedusing batch polymerization processes. If the polymerization is carriedout as a feed system the reaction can be carried out as follows. Thereactor is charged with the chosen medium, the chain transfer agent andoptionally a portion of the monomer(s). The remaining monomer(s) isplaced into a separate vessel. Initiator is dissolved or suspended inthe reaction medium in still another separate vessel. The medium in thereactor is heated and stirred while the monomer+medium andinitiator+medium are introduced over time, for example by a syringe pumpor other pumping device. The rate and duration of feed is determinedlargely by the quantity of solution the desired monomer/chain transferagent/initiator ratio and the rate of the polymerization. When the feedis complete, heating can be continued for an additional period.

[0164] Following completion of the polymerization, the polymer can beisolated by stripping off the medium and unreacted monomer(s) or byprecipitation with a non-solvent. Alternatively, the polymersolution/emulsion can be used as such, if appropriate to itsapplication. The applications for the S-(α,α′-disubstituted-α″-aceticacid) dithiocarbamate compounds include any of those listed hereinabovewith regard to the trithiocarbonate compounds.

[0165] Derivatives of the dithiocarbamate polymers or copolymers canalso be formed including esterification products from the alcohol and/ordiol end groups present. Thioesters can be formed utilizing mercaptan,and amides can be formed from amines, etc. Ammonium salts can be formedfrom primary, secondary, and tertiary amines. Metal salts can be formedfrom alkaline or alkaline earth hydroxides, oxides and the like.

[0166] The invention has wide applicability in the field of free radicalpolymerization and can be used to produce polymers and compositions forcoatings, including clear coats and base coat finishes for paints forautomobiles and other vehicles or industrial, architectural ormaintenance finishes for a wide variety of substrates. Such coatings canfurther include conventional additives such as pigments, durabilityagents, corrosion and oxidation inhibitors, rheology control agents,metallic flakes and other additives. Block, star, and branched polymerscan be used as compatibilizers, thermoplastic elastomers, dispersingagents or rheology control agents. Additional applications for polymersof the invention are in the fields of imaging, electronics (e.g.,photoresists), engineering plastics, adhesives, sealants, paper coatingsand treatments, textile coatings and treatments, inks and overprintvarnishes, and polymers in general.

II. Alkoxy Dithiocarbonates

[0167] Yet another embodiment of the present invention relates to alkoxydithiocarbonate compounds having the following formulae:

[0168] wherein R¹² and R¹³ are as defined hereinabove;

[0169] wherein R¹⁴ is optionally substituted, and can be a linear orbranched alkyl having from 1 to about 12 carbon atoms; an aryl group,optionally saturated or unsaturated; an arylalkyl having from 7 to about18 carbon atoms; an acyl group; an alkenealkyl having from 3 to about 18carbon atoms; an alkene group; an alkylene group; an alkoxyalkyl;derived from a polyalkylene glycol; derived from a polyalkylene glycolmonoalkyl ether having from 3 to 200 carbon atoms; derived from apolyalkylene glycol monoaryl ether having from 3 to 200 carbon atoms; apolyfluoroalkyl such as 2-trifluoroethyl; a phosphorous containingalkyl; or a substituted or unsubstituted aryl ring containingheteroatoms. Alkyl and alkylene groups from 1 to 6 carbon atoms arepreferred;

[0170] wherein the R¹⁴ substituents comprise an alkyl having from 1 to 6carbon atoms; an aryl; a halogen such as fluorine or chlorine; a cyanogroup; an amino group; an alkene group; an alkoxycarbonyl group; anaryloxycarbonyl group; a carboxy group; an acyloxy group; a carbamoylgroup; an alkylcarbonyl group; an alkylarylcarbonyl group; anarylcarbonyl group; an arylalkylcarbonyl group; a phthalimido group; amaleimido group; a succinimido group; amidino group; guanidimo group;allyl group; epoxy group; alkoxy group; an alkali metal salt; a cationicsubstitutent such as a quaternary ammonium salt; a hydroxyl group; anether having a total of from 2 to about 20 carbon atoms such as methoxy,or hexanoxy; a nitro; sulfur; phosphorous; a carboalkoxy group; aheterocyclic group containing one or more sulfur, oxygen or nitrogenatoms, or combinations thereof; and wherein “a” is 1 to about 4 with 1or 2 preferred.

[0171] The compounds of the above formula are generally identified asO-alkyl-S-(α,α′-disubstituted-α″-acetic acid) xanthates. TheO-alkyl-S-(α,α′-disubstituted-α″-acetic acid) xanthates are generated asthe reaction product of an alkoxylate salt, carbon disulfide, ahaloform, and a ketone. Alternatively, a metal salt of xanthate can beutilized in place of the alkoxylate salt and carbon disulfide.

[0172] The alkoxylate salt or carbon disulfide, or alternatively themetal salt of xanthate are typically the limiting agents for thereaction. The haloform is utilized in the reaction in an amountgenerally from 0 percent to about 500 percent molar excess, andpreferably from about 50 to about 200 percent molar excess. The ketoneis utilized in the reaction in an amount generally from 0 percent toabout 3000 percent molar excess, and preferably from about 100 percentto about 1000 percent molar excess. The metal hydroxide when utilized,is present in an amount from 10 percent to 500 percent molar excess,with about 60 percent to 150 percent molar excess preferred.

[0173] The general reaction mechanism for forming theO-alkyl-S-(α,α′-disubstituted-α″-acetic acid) xanthates is as follows:

[0174] The preparation of the O-alkyl-S-(α,α′-disubstituted-α″-aceticacid) xanthates begins with the addition of a xanthate, i.e., a salt ofxanthic acid to a reaction vessel, preferably equipped with an agitatingdevice, thermometer, addition funnel, and a condenser. The xanthate canbe prepared from an alkoxylate salt and carbon disulfide as known in theart.

[0175] For example, the sodium salt of O-ethyl xanthate,CH₃CH₂OC(S)S⁻Na⁺, can be prepared from sodium ethoxide and carbondisulfide in the presence of a solvent such as an acetone, andoptionally a catalyst, such as Aliquot 336 or other catalyst statedherein or known in the art, in a reaction vessel, preferably at about 0°to about 25° C. The general reaction is:

[0176] The metal salt of O-ethyl xanthate is also commercially availablefrom sources such as Aldrich Chemical of Milwaukee, Wis.

[0177] In a further step, a ketone, a haloform, optionally a solvent,and a catalyst, all as described hereinabove, are added to the reactionvessel containing the xanthate metal salt. When the ketone is used asthe solvent, the catalyst is optionally eliminated from the process. Astrong base as noted hereinabove is added to the mixture, preferablyover an extended period of time. The reaction components are preferablymixed throughout the reaction. The reaction product is subsequentlyacidified with an acid as noted hereinabove, completing the reaction andforming the O-alkyl-S-(α,α′-disubstituted-α″-acetic acid) xanthate. Thereaction is conducted at a temperature generally from about 0° C. toabout 80° C., and preferably from about 15° C. to about 50° C., withroom temperature being preferred. The reaction can be performed atatmospheric pressure under an inert atmosphere. The reaction timegenerally depends on temperature, and generally is complete within 20hours, and preferably within 10 hours. An α-trihalomethyl-α-alkanol canbe utilized in place of a haloform and ketone, as noted hereinabove withregard to the trithiocarbonate compounds.

[0178] The O-alkyl-S-(α,α′-disubstituted-α″-acetic acid) xanthates canbe utilized as an initiator to initiate or start the polymerization of amonomer, as a chain transfer agent which interrupts and terminates thegrowth of a polymer chain by formation of a new radical which can act asthe nucleus for forming a new polymer chain, and/or as a terminatorwhich are incorporated into a polymer as a dormant species. Preferably,the O-alkyl-S-(α,α′-disubstituted-α″-acetic acid) xanthates are utilizedas chain transfer agents in free radical polymerizations having livingcharacteristics to provide polymers of controlled molecular weight andlow polydispersity.

Xanthate (Co)Polymers

[0179] Polymers or copolymers of the following formulas can be preparedfrom the O-alkyl-S-(α,α′-disubstituted-α″-acetic acid) xanthates:

[0180] wherein a, R¹², R¹³, and R¹⁴ are as defined hereinabove, whereinthe polymer is derived from a conjugated diene monomer, or a vinylcontaining monomer, or combinations thereof, as defined hereinabove andincorporated by reference, and wherein each g repeat unit,independently, is the same or different and is generally from 1 to about10,000, and preferably from about 5 to about 500. Preferred monomers arealkyl acrylates, acrylic acid, and styrene. Of course, it is to beunderstood that when g is 1, the polymer is a single reacted monomerunit.

[0181] The above polymers or copolymers can be prepared by bringing intocontact with each other the monomer(s) which formO-alkyl-S-(α,α′-disubstituted-α″-acetic acid) xanthate compound, andoptionally a) solvent, and b) a radical polymerization initiator; insuitable amounts, as described hereinabove.

[0182] It is believed the mechanism is as follows:

[0183] As illustrated by the above mechanism, the monomers arepolymerized into the xanthate compounds adjacent to the thiocarbonylthiolinkage, between the single bonded sulfur atom and the tertiary carbonatom of the compound.

[0184] The O-alkyl dithiocarbonate compounds of the present inventioncan be used to produce polymers which are substantially colorless. Thepolymers or copolymers of the O-alkyl dithiocarbanate compounds are morehydrolytically stable because the electro-donating amino groups renderthe thiocarbonyl group less electrophilic and the polymers are stabletoward nucleophiles such as amines.

[0185] The reaction conditions are chosen as known to one skilled in theart so that the temperature utilized will generate a radical in acontrolled fashion, wherein the temperature is generally from about roomtemperature to about 200° C. The reaction can be performed attemperatures lower than room temperature, but it is impractical to doso. The temperature often depends on the initiator chosen for thereaction, for example, when AIBN is utilized, the temperature generallyis from about 40° C. to about 80° C., when azodicyanodivaleric acid isutilized, the temperature generally is from about 50° C. to about 90°C., when di-t-butylperoxide is utilized, the temperature generally isfrom about 110° C. to about 160° C., and whenO-alkyl-S-(α,α′-disubstituted-α″-acetic acid) xanthate is utilized, thetemperature is generally from about 80° C. to about 200° C.

[0186] As noted above with respect to the dithiocarbamate compounds, thepolymers or copolymers prepared from theO-alkyl-S-(α,α′-disubstituted-α″-acetic acid) xanthate contain reactiveend groups which are able to further undergo chemical transformation orreaction in order to be joined with another polymer chain, in order toform extended copolymers for example. The process of the invention canbe carried out, for example, in emulsion solution or suspension ineither a batch, semi-batch, continuous, bulk or feed mode.

[0187] Conventional procedures can be used to produce narrowpolydispersity polymers. For lowest polydispersity polymers, the chaintransfer agent is added before polymerization is commenced. Thepolydispersity of the xanthate polymers or copolymers is generally lessthan about 3.0. For example, when carried out in batch mode in solution,the reactor is typically charged with chain transfer agent and monomeror medium plus monomer. The desired amount of initiator is then added tothe mixture and the mixture is heated for a time which is dictated bythe desired conversion and molecular weight. Polymers with broad, yetcontrolled, polydispersity or with multimodal molecular weightdistribution can be produced by controlled addition of the chaintransfer agent over the course of the polymerization process.

[0188] In the case of emulsion or suspension polymerization the mediumwill often be predominately water and the conventional stabilizers,dispersants and other additives can be present. For solutionpolymerization, the reaction medium can be chosen from a wide range ofmedia to suit the monomer(s) being used.

[0189] As already stated, the use of feed polymerization conditionsallows the use of chain transfer agents with lower transfer constantsand allows the synthesis of block polymers that are not readily achievedusing batch polymerization processes. If the polymerization is carriedout as a feed system the reaction can be carried out as follows. Thereactor is charged with the chosen medium, the chain transfer agent andoptionally a portion of the monomer(s). The remaining monomer(s) isplaced into a separate vessel. Initiator is dissolved or suspended inthe reaction medium in another separate vessel. The medium in thereactor is heated and stirred while the monomer+medium andinitiator+medium are introduced over time, for example by a syringe pumpor other pumping device. The rate and duration of feed is determinedlargely by the quantity of solution the desired monomer/chain transferagent/initiator ratio and the rate of the polymerization. When the feedis complete, heating can be continued for an additional period.

[0190] Following completion of the polymerization, the polymer can beisolated by stripping off the medium and unreacted monomer(s) or byprecipitation with a non-solvent. Alternatively, the polymersolution/emulsion can be used as such, if appropriate to itsapplication. The applications for theO-alkyl-S-(α,α′-disubstituted-α″-acetic acid) xanthate dithiocarbonatecompounds include any of those listed hereinabove with regard to thetrithiocarbonate and dithiocarbamate compounds.

[0191] The dithiocarbonate compounds of the invention have wideapplicability in the field of free radical polymerization and can beused as thickeners and to produce polymers and compositions forcoatings, including clear coats and base coat finishes for paints forautomobiles and other vehicles or industrial, architectural ormaintenance finishes for a wide variety of substrates. Such coatings canfurther include pigments, durability agents, corrosion and oxidationinhibitors, rheology control agents, metallic flakes and otheradditives. Block and star, and branched polymers can be used ascompatibilizers, thermoplastic elastomers, dispersing agents or rheologycontrol agents. Additional applications for polymers of the inventionare composites, potting resins, foams, laminate, in the fields ofimaging, electronics (e.g., photoresists), engineering plastics,adhesives, sealants, paper coatings and treatments, textile coatings andtreatments, inks and overprint varnishes, and polymers in general, andthe like.

[0192] The present invention will be better understood by reference tothe following examples which serve to describe, but not to limit, thepresent invention.

EXAMPLES Example 1

[0193] Synthesis of s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonate, (R¹=R²=CH₃)

[0194] Procedure:

[0195] In a 500 ml jacketed flask equipped with a mechanical stirrer, athermometer, a reflux condenser and an addition funnel added 22.9 gramsof carbon disulfide, 2.0 gram of tetrabutylammonium bisulfate and 100 mltoluene. The solution was stirred at 20° C. under nitrogen and 168 gramsof 50% sodium hydroxide solution was added dropwise to keep thetemperature between 20-30° C. 30 min. after the addition, a solution of43.6 grams of acetone and 89.6 grams of chloroform was added at 20-30°C. The reaction was then stirred at 15-20° C. overnight. 500 ml waterwas added to the mixture, the layers were separated. The organic layerwas discarded and the aqueous layer was acidified with concentrated HClto precipitate the product as yellow solid. 50 ml toluene was added tostir with the mixture. Filtered and rinsed the solid with toluene tocollect 22.5 grams of product after drying in the air to constantweight.

Example 2

[0196] Synthesis of s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonates. (R¹=R²=CH₃)

[0197] The procedure was essentially the same as in example 1, exceptthat mineral spirits replaced toluene as solvent. 40.3 grams of productwas obtained as yellow solid.

Example 3

[0198] Synthesis of s-alkyl-s′-(-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonates

[0199] Procedure:

[0200] Dodecylmercaptan (0.1 mole), and Aliquot 336 (0.004 mole) wasdissolved in 48 g acetone. 50% sodium hydroxide solution (0.105 mole)was added, followed by dropwise addition of carbon disufide (0-1 mole)in 10 g acetone solution. The media turned from colorless to yellow.After 20 min., chloroform (0.15 mole) was added followed by dropwiseaddition of 50% NaOH (0.5 mole) and 5 g NaOH beads. The rxn was stirredat 15-20° C. overnight, filtered and the sol. was rinsed with acetone.The acetone layer was concentrated to dryness. The mass was dissolved inwater, acidified with concentrated HCl to precipitate the product,rinsed with water to collect the yellow solid. The solid was dissolvedin 350 ml hexanes. The solution was dried over magnesium sulfate andfiltered. The organic solution was cooled to precipitate the product asyellow flakes. Yield is 85%.

Example 4

[0201] Polymerization of Prior Art Compounds

[0202] polyacrylate acetone

[0203] Procedure:

[0204] Dibenzyltrithiocarbonate (1.54 g, 5.3 mmole),2-ethylhexylacrylate (25 grams 135.7 mmole), AIBN (0.05 g, 0.3 mmole)and acetone (25 ml) were mixed. 1 ml of undecane was added as GCinternal standard for calculating the conversion. The solution waspurged with nitrogen for 15 min. before heating to 52° C. undernitrogen. No exotherm was detected throughout the reaction. Aliquots ofthe sample were taken for GC and GPA analyses during the course of thepolymerization. The following table showed the progress of thepolymerization in 7 hours. Sample Time (mins.) Mn Mw Conv. % 1 2 120 866970 3.7 3 270 1180 1428 13.2 4 420 1614 2059 26.9

Example 5

[0205] Polymerization with s,s′-bis-(α,α′-disubstituted-α″-aceticacid)-trithiocarbonates

[0206] Procedure:

[0207] Following the same procedure as in example 4, the noveltricarbonate (1.50 g, 5.3 mmole), 2-ethylhexylacrylate (25 g, 135.7mmole), AIBN (0.05 g, 0.3 mmole) and acetone (25 ml) were mixed. 1 ml ofundecane was added as internal standard The reaction was stirred at 52°C. for 7 hours. The following table showed the conversion and themolecular weights of the resulting polymer. Sample Time (mins.) Mn MwConv. % 1  45  669  724 3.5 2 120 1433 1590 25.8 3 240 3095 3621 79.8 4300 3345 3898 87.9 5 420 3527 4136 93.9

Example 6

[0208] Polymerization with s,s′-bis-(α,α′-disubstituted-α″-acetic acid)Trithiocarbonates.

[0209] Procedure:

[0210] This is a bulk polymerization with the trithiocarbonate aschain-transfer agent The trithiocarbonate (1.0 g, 3.5 mmole),2-ethylhexylacrylate (25 g, 135.7 mmole), AIBN (0.05 g, 0.3 mmole) and 1ml undecane (internal standard) were purged with nitrogen, then heatedto 60° C. for 3 hours. The following table showed the conversion and themolecular weight of the polymer. Sample Time (mins.) Mn Mw Conv. % 1 302229 2616 35.6 2 90 4501 5526 91.9 3 180 4672 5780 97.8

Example 7

[0211] Polymerization with s,s′-bis-(α,α′-disubstituted-α″-acetic acid)Trithiocarbonates.

[0212] Procedure:

[0213] The trithiocarbonate was used as inifertor. Trithiocarbonate (1.0g, 3.5 mmole), n-butylacrylate (20 g, 156.1 mmole) with 1 ml decane asinternal standard were purged with nitrogen for 15 min., thenpolymerized at 130° C. under nitrogen for 6 hours. The following tableshowed the conversion and the molecular weights of the polymer. SampleTime (mins.) Mn Mw Conv. % 1  60 1118 1242 16.0 2 120 1891 2199 32.5 3240 2985 3337 52.5 4 360 3532 4066 65.7

Example 8

[0214] Free Radical Polymerization Utilizings,s′-bis-(α,α′-disubstituted-α″-acetic acid)-trithiocarbonates asInifertor.

[0215] Procedure:

[0216] The trithiocarbonate (2.0 g, 7.1 mmole) and 2-ethylhexylacrylate(25.0 g, 135.7 mmole) were purged with nitrogen for 15 min then heatedto 175° C. for 10 hours. The following table showed the conversion andmolecular weighs of the polymer. Sample Time (mins.) Mn Mw Conversion 140 1006 1117 24.2 2 90 1446 1699 42.0 3 150 1750 2241 51.9 4 600 21853115 98.9

Example 9

[0217] Polymerization with s,s′-bis-(α,α′-disubstituted-α″-acetic acid)Trithiocarbonates.

[0218] Procedure:

[0219] The trithiocarbonate was used as inifertor to make polystyrene.The trithiocarbonate (2.0 g, 7.1 mmole) and styrene (25 g, 240.4 mmole)with 1 ml decane as internal standard were polymerized at 140° C. undernitrogen for 6 hours. The following table showed the progress of thepolymerization. Sample Time (mins.) Mn Mw Conv. % 1 30 613 648  9.5 2 60779 831 16.9 3 120 1829 2071 53.9 4 300 2221 2559 72.3 5 360 2537 295684.5

Example 10

[0220] Polymerization with s,s′-bis-(α,α′-disubstituted-α″-acetic acid)Trithiocarbonates.

[0221] Procedure:

[0222] The trithiocarbonate was used as chain-transfer agent to makeblock copolymers of 2-ethylhexylacrylate and styrene. Thetrithiocarbonate (1.5 g, 5.3 mmole), 2-ethylhexylacrylate (30 g, 162.8mmole) and AIBN (0.03 g, 0.18 mmole) with 1 ml undecane as the internalstandard were polymerized at 60° C. under nitrogen as before. 6.5 hourslater, styrene (15 g, 144.2 mmole) and AIBN (0.03 g, 0.18 mmole) wasadded. The polymerization continued and the following shows theprogress. Sample Time (mins.) Mn Mw Conv. % 1  70 1922 2459 32.5 2 1353556 4204 80.8 3 270 4095 4874 95.0 4  330* 4407 5025 96.6 5 1290  48345969 —

Example 11

[0223] Polymerization with the trithiocarbonate from example 3. Thetrithiocarbonate (1.82 g. 5 mmole), n-butyl acrylate (25 g, 195.1 mmole)and AIBN (0.04 g, 0.25 mmole) with 1 ml undecane as the internalstandard were polymerized under nitrogen atmosphere for 7 hours. Itshowed 97.5% conversion by GC as depicted in the following table: SampleTime (min) Mn Mw Pd % Conv. 1  60 2177 2792 1.26 46.2 2 120 2758 38651.40 67.1 3 420 3786 5439 1.44 97.5

Example 12

[0224]

[0225] Procedure:

[0226] In a 300 ml jacketed flask equipped with a mechanical stirrer,thermometer, addition funnel and nitrogen-inlet tube (for inerting) 16.3grams potassium O-ethylxanthate, 17.9 grams chloroform, 1.36 gramstetrabutylammonium hydrogen sulfate and 88.1 grams cyclohexanone wereplaced and cooled to between 15-20° C. 40 grams of sodium hydroxidebeads were added in portions to keep the temperature below 25° C. Afterthe addition, the reaction was stirred at about 20° C. for 12 hours. 100ml of water was added and the aqueous layers were acidified withconcentrated hydrochloric acid. 100 ml toluene was added to extract theproduct. After drying the toluene solution with magnesium sulfate, itwas filtered and concentrated to afford 20 grams of yellow solid whichwas further purified by recrystallizing from hexanes.

Example 13

[0227]

[0228] In this example, sodium O-ethylxanthate was formed in situ. 7.6grams carbon disulfide, 1 gram tetrabutylammonium hydrogen sulfate and58.1 grams acetone were stirred in a reaction vessel as equipped abovein Example 12. 7.1 grams sodium ethoxide (96%, Aldrich) was added inportions at room temperature. 30 minutes after the addition, 17.9 gramschloroform was added followed by 20 grams sodium hydroxide beads inportions to keep the temperature below 25° C. Stirred at 15° C. for 12hours. The mixture was filtered and rinsed thoroughly with acetone. Theacetone solution was concentrated and dissolved in water. 20 mlconcentrated HCl was added. The oil formed was extracted into two 50 mlportions of toluene, dried over magnesium sulfate, and concentrated intoan oil. The oil was extracted with two 50 ml portions of boiling hexane.Beige-colored solid was produced from the solution.

Example 14

[0229] Synthesis of S-(methyl, methyl, acetic acid) Dithiocarbamate

[0230] Procedure:

[0231] 10.7 grams sodium N,N-diphenyldithiocarbamate, 7.2 gramschloroform, 4.6 grams acetone, 0.8 gram Aliquot 336 and 50 ml toluenewere stirred at 15-20° C. under nitrogen while 16 grams 50% sodiumhydroxide was added dropwise to keep the reaction temperature below 20°C. The reaction was stirred for 12 hours. Water was added to dissolvethe solid. The layers were separated and the aqueous layer was acidifiedwith concentrated hydrochloric acid. The solid was washed with water andrecrystallized from toluene to afford light-yellow colored solid.

Example 15

[0232]

[0233] Procedure:

[0234] Sodium N,N-diphenyldithiocarbamate was replaced by sodiumN,N-hexamethylenedithiocarbamate and the reaction was conducted asexplained in Example 14. The product was a white solid.

Example 16

[0235]

[0236] Procedure:

[0237] The sodium dithiocarbamate utilized in this example was sodiummorpholinodithiocarbamate. The reaction was conducted as explained inExample 14. The product was afforded in good yield as white powders.

Example 17

[0238]

[0239] Procedure:

[0240] The sodium dithiocarbamate utilized in this example was sodiumN,N-diethyl dithiocarbamate. The reaction was conducted as explained inExample 14 and acetone was replaced by cyclohexanone. The product wasafforded in good yield as white powders.

Example 18

[0241]

[0242] Procedure:

[0243] Sodium N,N-dibutyldithiocarbamate was utilized in this example.The reaction was conducted as described in Example 14. The product wasisolated as white powder.

Example 19

[0244]

[0245] Procedure:

[0246] Sodium N,N-di-isobutyldithiocarbamate was utilized in thisexample. The reaction was conducted as described in Example 14. Theproduct was isolated as yellow solid.

Example 20

[0247]

[0248] Procedure:

[0249] Sodium N,N-hexamethylene dithiocarbamate, 2-butanone was utilizedin this example. The reaction was conducted as explained in Example 14and was replaced by acetone. The product was afforded in good yield aswhite powder after recrystallization from hexane/toluene.

Example 21

[0250]

[0251] Procedure:

[0252] 14.1 grams of S,S′-disodium salt of the piperazinebis-(dithiocarbamic acid), 100 ml 2-butanone, 17.9 grams chloroform and1.13 grams benzyltriethylammonium chloride were mixed and stirred at15-20° C. under nitrogen atmosphere. 40 grams 50% sodium hydroxidesolution was added in portions to keep the reaction temperature under20° C. After the addition, the reaction was allowed to stir at 20° C.for 12 hours. The mixture was filtered and the solid was rinsed with2-butanone and then stirred with 100 ml water. Concentrated HCl wasadded until water turned acidic. The solid was collected and rinsed withwater, to yield off-white colored powders. The powder was crystallizedwith methanol to afford white powder.

Example 22

[0253]

[0254] As in the above procedure of Example 21 the disodium salt ofpiperizine bis-(dithiocarbamic acid) was replaced with sodiumdiethyldithiocarbamate, and 2-butanone with acetone. The desired productwas obtained as white powders in high yield.

Example 23

[0255]

[0256] The procedure of Example 21 was utilized and the disodium saltsof piperizine bis-(dithiocarbamic acid) was replaced by sodiumdimethyldithiocarbamate, and BTEAC was replaced by tetrabutylammoniumhydrogensulfate, the desired product was obtained as white powders.

Example 24

[0257]

[0258] The reaction was performed as in Example 21, but thedithiocarbamate salt was sodium N-phenyl-N−1-naphthyl dithiocarbamate,and the ketone was acetone. The product was obtained as beige-coloredpowders after recrystallization from a mixture of toluene and heptane.

Example 25

[0259]

[0260] The reaction was performed in a similar manner as in Example 21,but 2-butanone was replaced by 2-pentanone, the product was whitepowders after recrystallization from hexanes.

Example 26

[0261]

[0262] Procedure:

[0263] 7.38 grams diethylamine and 80 ml acetone and 2.0 grams Aliquot336 were mixed and stirred under nitrogen atmosphere at 15° C. 7.6 gramscarbon disulfide in 20 ml acetone was added dropwise to keep thetemperature below 20° C. 30 minutes after the addition, 8.8 grams 50%sodium hydroxide was added. 30 minutes later, 17.9 grams chloroform wasadded followed by 31.2 grams 50% sodium hydroxide. The reaction wasallowed to stir at 15-20° C. for 12 hours. The mixture was concentratedand then dissolved in water. 15 ml concentrated HCl was added toprecipitate a beige-colored solid which was washed thoroughly with water(20 grams). Recrystallization from toluene afforded white solid.

Example 27

[0264]

[0265] Procedure:

[0266] The diethylamine of the procedure of Example 26 was replaced byhexamethyleneimine and acetone was replaced by methyl isobutyl ketone.The product was recrystallized from hexane/toluene to afford whitepowders.

Example 28

[0267]

[0268] The diethylamine of the procedure of Example 26 was replaced bydiallylamine and Aliquot® 336 was replaced by BTEAC. The product waswhite crystalline solid after recrystallization from hexane/toluene.

Example 29

[0269]

[0270] The diethylamine of the procedure of Example 26 was replaced bydimethyl-amine (40% in water). The product was white crystals afterrecrystallization from toluene.

Example 30

[0271]

[0272] The acetone of the procedure of Example 27 was replaced by2-butanone. The produce was a white solid after recrystallization fromtoluene.

Example 31

[0273]

[0274] The acetone of the procedure of Example 26 was replaced bycyclohexanone. The product was white solid after recrystallization fromtoluene.

Example 32

[0275]

[0276] In this example, 22.8 grams of sodium N-phenyl-N-4-anlinophenyldithiocarbamate, 17.9 grams chloroform and 100 ml acetone were mixed andstirred at 15° C. under nitrogen. 40 grams 50% sodium hydroxide wasadded dropwise in to keep the temperature under 20° C. The reaction wasallowed to stir overnight (approximately 12 hours) at 15° C. Solvent wasremoved in a rotary evaporator and the residue was dissolved in water.The aqueous solution was acidified with concentrated hydrochloric acidto collect a green-colored solid. The dried solid was recrystallizedfrom toluene to afford grayish-colored solid. The structure wasconfirmed by H-NMR.

Example 33

[0277] Controlled Radical Polymerization with Novel DithiocarbonateDerivatives

[0278] The theoretical number-averaged molecular (Mn)_(theo) weight foreach polymer or copolymer was calculated from the formula XII (a)assuming 100% conversion.

[0279] (Mn)_(ex) is the Mn measured by GPC from polymerization products.In bulk polymerization, 20-25 grams of monomer, 0.01-0.05 grams of aninitiator such as AIBN and the amount of the dithiocarbonate as neededto give desired Mn (calculated using formula XII(a)) are purged withnitrogen gas, then heated to temperature gradually. Sometimes air orwater-cooling is necessary to keep the temperature under 83° C. Theresulting polymers were subjected to MALDI mass spectrum measurement.The spectrum clearly showed the carboxyl-terminating group in everypolymer chain.

[0280] Block copolymerization was performed by making the first polymerin bulk, then add the second monomer and same amount of initiator, thenpolymerizing in the same manner. Random copolymerization could have beenperformed if both monomers were added at the same time.

[0281] The results of the polymerizations and block polymerizations arelisted in the following table. Dithiocarbonate Polymers DithiocarbonateTime/ Example Monomer Solvent Temp. (Mn)_(ex) (Mn)_(theo) PD HourControl Butyl acrylate — >100,000 >3 1 12 Butyl acrylate MEK 80 37775000 1.78 5 26 Styrene none-bulk polym. 140  7830 5000 2.05 5 17 Butylacrylate MEK 80 1645 2000 2.07 5 14 Butyl acrylate MEK 75 4656 5000 1.315 21 Butyl acrylate MEK 80 3049 3000 1.32 6 19 Butyl acrylate MEK 803683 3000 2.03 6 13 Ethyl acrylate none-bulk polym. 65 5564 10000  1.835 29 Vinyl acetate none-bulk polym. 70 4367 5000 1.47 5 15t-butylacrylamide THF 70 3622 5000 1.91 5 24 Butyl acrylate none-bulkpolym. 80 5093 5000 1.36 6.5 32 Butyl acrylate MEK 80 2061 5000 1.61 2.5Block Copolymers Dithiocarbonate Example Monomer-1 (Mn)_(ex) (Mn)_(theo)PD Monomer-2 (Mn)_(ex) (Mn)_(theo) PD 30 Butyl acrylate 1695 1798 1.92Vinyl acetate 1873 2540 1.87 31 Butyl acrylate 1631 1798 2.23 Vinylacetate 2014 2444 1.96

[0282] While in accordance with the patent statutes the best mode andpreferred embodiment have been set forth, the scope of the invention isnot limited thereto, but rather by the scope of the attached claims.

What is claimed is:
 1. A composition, comprising: a dithiocarbamatecompound having the formula:

wherein j is 1 or 2; wherein R¹² and R¹³, independently, is the same ordifferent, is optionally substituted, and is a linear or branched alkylhaving from 1 to about 12 carbon atoms; or an aryl group having from 6to about 18 carbon atoms, optionally containing heteroatoms; or R¹² andR¹³ can form and be part of a substituted or unsubstituted cyclic ringhaving from 3 to about 12 carbon atoms; with the proviso that when j is1, T is NR¹⁵R¹⁶), and when j is 2, T is a divalent radical having anitrogen atom directly connected to each carbon atom of the twothiocarbonyl groups; and wherein R¹⁵ and R¹⁶, independently, is the sameor different, optionally substituted, optionally contains heteroatoms,and is hydrogen; or a linear or branched alkyl having from 1 to about 18carbons; or an aryl group or an aryl alkyl group having from 6 to about18 carbon atoms, optionally saturated or unsaturated; or an arylalkylhaving from 7 to about 18 carbons; or an alkenealkyl having from 3 toabout 18 carbon atoms; or derived from polyalkylene glycol ether; orderived from an amine; or R¹⁵ and R¹⁶ are in the form of a substitutedor unsubstituted cyclic ring with the nitrogen atom having a total of 4to about 12 carbon atoms.
 2. A composition according to claim 1, whereinj is 1, and wherein R¹² and R¹³, independently, is a phenyl group, or analkyl group having 1 to about 10 carbon atoms, or wherein R¹² and R¹³are part of said cyclic ring.
 3. A composition according to claim 1,wherein j is 1, and wherein R¹⁵ and R¹⁶, independently, is a phenylgroup, or an alkyl group having from 1 to about 10 carbon atoms, orhexamethylene, or wherein R¹⁵ and R¹⁶ are part of said cyclic ring.
 4. Acomposition according to claim 2, wherein R¹⁵ and R¹⁶, independently, isa phenyl group, or an alkyl group having from 1 to about 10 carbonatoms, or hexamethylene, or wherein R¹⁵ and R¹⁶ are part of said cyclicring.
 5. A composition according to claim 4, wherein R¹² and R¹³independently, is an alkyl having from 1 to about 4 carbon atoms, orwherein R¹² and R¹³ are part of said cyclic ring.
 6. A compositionaccording to claim 1, wherein j is 2 and T is:

wherein R¹⁷ and R¹⁸, independently, is the same or different, isoptionally substituted, and is hydrogen; a linear or branched alkylhaving from 1 to about 18 carbon atoms; or an aryl group having fromabout 6 to about 18 carbon atoms; or an arylalkyl having from 7 to about18 carbon atoms; or a alkenealkyl having from 3 to about 18 carbonatoms; wherein R¹⁹ is optionally substituted, or is non-existent; or analkylene group having from 1 to about 18 carbon atoms; or derived from apolyalkylene glycol either having from 3 to about 200 carbon atoms; andwherein R²⁰ and R²¹, independently, is the same or different, and isoptionally substituted, and is an alkylene group having from 1 to about4 carbon atoms.
 7. A composition according to claim 1, wherein j is 2and wherein T is:

wherein n is 0 to about
 18. 8. A composition according to claim 6,wherein R¹² and R¹³, independently, is a phenyl group, or an alkyl grouphaving 1 to about 10 carbon atoms, or R¹² and R¹³ are part of a cyclicring having 3 to about 12 carbon atoms; and wherein R²⁰ and R²¹ have atotal of 3 to 5 carbon atoms.
 9. A composition according to claim 7,wherein R¹² and R¹³, independently, is a phenyl group, or an alkyl grouphaving 1 to about 10 carbon atoms, or R¹² and R¹³ are part of a cyclicring having from 3 to about 12 carbon atoms; and wherein n is 0 to about6.
 10. A composition, comprising: a dithiocarbamate polymer or copolymerhaving the formula:

wherein each R¹² and R¹³, independently, is the same or different, isoptionally substituted, and is a linear or branched alkyl having from 1to about 12 carbon atoms; or an aryl group having from 6 to about 18carbon atoms, optionally containing heteroatoms; or R¹² and R¹³ can formand be part of a substituted or unsubstituted cyclic ring having from 3to about 12 carbon atoms; wherein R¹⁵ and R¹⁶, independently, is thesame or different, optionally substituted, optionally containsheteroatoms, and is hydrogen; or a linear or branched alkyl having from1 to about 18 carbons; or an aryl group having from 6 to about 18 carbonatoms, optionally saturated or unsaturated; or an arylalkyl having from7 to about 18 carbons; or an alkenealkyl having from 3 to about 18carbon atoms; or derived from polyalkylene glycol ether; or derived froman amine; or R¹⁵ and R¹⁶ are in the form of a substituted orunsubstituted cyclic ring with the nitrogen atom having a total of 4 toabout 12 carbon atoms; wherein T is a divalent radical having a nitrogenatom directly connected to each carbon atom of the two thiocarbonylgroups; wherein said polymer repeat units are derived from at least oneconjugated diene monomer, or a vinyl containing monomer, or combinationsthereof, with the proviso that each repeat unit can be the same ordifferent; and wherein the number of said repeat units f, independently,is from 1 to about 10,000.
 11. A composition according to claim 10,wherein R¹² and R¹³, independently, is a phenyl group, or an alkyl grouphaving 1 to about 10 carbon atoms, or wherein R¹² and R¹³ are part of acyclic ring having from 3 to about 12 carbon atoms; and wherein R¹⁵ andR¹⁶, independently, is a phenyl group, or an alkyl group having from 1to about 10 carbon atoms, or hexamethylene, or wherein R¹⁵ and R¹⁶ arepart of a cyclic ring having from 3 to about 12 carbon atoms.
 12. Acomposition according to claim 11, wherein R¹² and R¹³ independently, isan alkyl having from 1 to about 4 carbon atoms, or wherein R¹² and R¹³are part of a cyclic ring having from 3 to about 12 carbon atoms.
 13. Acomposition according to claim 10, wherein T is:

wherein R¹⁷ and R¹⁸, independently, is the same or different, isoptionally substituted, and is hydrogen; or a linear or branched alkylhaving from 1 to about 18 carbon atoms; or an aryl group having fromabout 0.6 to about 18 carbon atoms; or an arylalkyl having from 7 toabout 18 carbon atoms; or a alkenealkyl having from 3 to about 18 carbonatoms; wherein R¹⁹ is optionally substituted, or is non-existent; or analkylene group having from 1 to about 18 carbon atoms; or derived from apolyalkylene glycol either having from 3 to about 200 carbon atoms;wherein R²⁰ and R²¹, independently, is the same or different, and isoptionally substituted, and is an alkylene group having from 1 to about4 carbon atoms, or wherein T is:

wherein n is 0 to about
 18. 14. A composition according to claim 13,wherein R¹² and R¹³, independently, is a phenyl group, or an alkyl grouphaving 1 to about 10 carbon atoms, or R¹² and R¹³ are part of a cyclicring having from 3 to about 12 carbon atoms; and wherein R²⁰ and R²¹have a total of 3 to 5 carbon atoms; and wherein n is 0 to about
 6. 15.A composition according to claim 10, wherein said conjugated dienemonomer has from 4 to 12 carbon atoms, and wherein said vinyl containingmonomer has the formula:

wherein R³ comprises hydrogen, halogen, C₁-C₄ alkyl, or substitutedC₁-C₄ alkyl wherein said substituents, independently, comprise one ormore hydroxy, alkoxy, aryloxy(OR⁵), carboxy, metal carboxylate (COOM)with M being sodium, potassium, calcium, zinc or an ammonium salt,acyloxy, aroyloxy(O₂CR⁵), alkoxy-carbonyl(CO₂R⁵), aryloxy-carbonyl; orN-pyrrolidonyl; wherein R⁴ comprises hydrogen, R⁵, CO₂H, CO₂R⁵, COR⁵,CN, CONH₂, CONHR⁵, O₂CR⁵, OR⁵ or halogen; and wherein R⁵ comprisesC₁-C₁₈ alkyl, substituted C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, aryl,heterocyclyl, aralkyl, or alkaryl, and wherein said substituents,independently, comprise one or more epoxy, hydroxy, alkoxy, acyl,acyloxy, carboxy, carboxy salts, sulfonic acid, sulfonic salts, alkoxy-or aryloxy-carbonyl, dicyanato, cyano, silyl, halo or dialkylamino. 16.A composition according to claim 11, wherein said conjugated dienemonomer has from 4 to 12 carbon atoms, and wherein said vinyl containingmonomer has the formula:

wherein R³ comprises hydrogen, halogen, C₁-C₄ alkyl, or substitutedC₁-C₄ alkyl wherein said substituents, independently, comprise one ormore hydroxy, alkoxy, aryloxy(OR⁵), carboxy, metal carboxylate (COOM)with M being sodium, potassium, calcium, zinc or an ammonium salt,acyloxy, aroyloxy(O₂CR⁵), alkoxy-carbonyl(CO₂R⁵), aryloxy-carbonyl; orN-pyrrolidonyl; wherein R⁴ comprises hydrogen, R⁵, CO₂H, CO₂R⁵, COR⁵,CN, CONH₂, CONHR⁵, O₂CR⁵, OR⁵ or halogen; and wherein R⁵ comprisesC₁-C₁₈ alkyl, substituted C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, aryl,heterocyclyl, aralkyl, or alkaryl, and wherein said substituents,independently, comprise one or more epoxy, hydroxy, alkoxy, acyl,acyloxy, carboxy, carboxy salts, sulfonic acid, sulfonic salts, alkoxy-or aryloxy-carbonyl, dicyanato, cyano, silyl, halo or dialkylamino. 17.A composition according to claim 13, wherein said conjugated dienemonomer has from 4 to 12 carbon atoms, and wherein said vinyl containingmonomer has the formula:

wherein R³ comprises hydrogen, halogen, C₁-C₄ alkyl, or substitutedC₁-C₄ alkyl wherein said substituents, independently, comprise one ormore hydroxy, alkoxy, aryloxy(OR⁵), carboxy, metal carboxylate (COOM)with M being sodium, potassium, calcium, zinc or an ammonium salt,acyloxy, aroyloxy(O₂CR⁵), alkoxy-carbonyl(CO₂R⁵), aryloxy-carbonyl; orN-pyrrolidonyl; wherein R⁴ comprises hydrogen, R⁵, CO₂H, CO₂R⁵, COR⁵,CN, CONH₂, CONHR⁵, O₂CR⁵, OR⁵ or halogen; and wherein R⁵ comprisesC₁-C₁₈ alkyl, substituted C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, aryl,heterocyclyl, aralkyl, or alkaryl, and wherein said substituents,independently, comprise one or more epoxy, hydroxy, alkoxy, acyl,acyloxy, carboxy, carboxy salts, sulfonic acid, sulfonic salts, alkoxy-or aryloxy-carbonyl, dicyanato, cyano, silyl, halo or dialkylamino. 18.A composition according to claim 15, wherein said polymer repeat unit isderived from alkyl acrylate, vinyl acetate, acrylic acid, or styrene,N-vinyl pyrrolidone or a combination thereof, and wherein said number ofrepeat units f is from about 3 to about 5,000.
 19. A compositionaccording to claim 16, wherein said polymer repeat unit is derived fromalkyl acrylate, vinyl acetate, acrylic acid, or styrene, N-vinylpyrrolidone or a combination thereof, and wherein said number of repeatunits f is from about 3 to about 5,000.
 20. A composition according toclaim 17, wherein said polymer repeat unit is derived from alkylacrylate, vinyl acetate, acrylic acid, or styrene, N-vinyl pyrrolidoneor a combination thereof, and wherein said number of repeat units f isfrom about 3 to about 5,000.
 21. A method for forming a dithiocarbamatecompound, comprising the steps of: reacting a metal salt of adithiocarbamate, a haloform, and a ketone in the presence of a base, andoptionally a solvent and a catalyst, to form a reaction product; andacidifying said reaction product to form said dithiocarbamate compound.22. A method according to claim 21, wherein said reaction is conductedat a temperature from about minus 15° C. to about 80° C.
 23. A methodaccording to claim 22, wherein said haloform is chloroform or bromoform,or a blend thereof, and wherein said ketone has the formula:

wherein R¹² and R¹³, independently, can be the same or different, canoptionally be substituted, and can be a linear or branched alkyl havingfrom 1 to about 12 carbon atoms; or an aryl group having from 6 to about18 carbon atoms, optionally containing heteroatoms; or R¹² and R¹³ canform and be part of a substituted or unsubstituted cyclic ring havingfrom 3 to about 12 carbon atoms.
 24. A method according to claim 23,including said catalyst.
 25. A method according to claim 23, whereinsaid dithiocarbamate has the formula:

wherein j is 1 or 2; wherein R¹² and R¹³, independently, is the same ordifferent, is optionally substituted, and is a linear or branched alkylhaving from 1 to about 12 carbon atoms; or an aryl group having from 6to about 18 carbon atoms, optionally containing heteroatoms; or R¹² andR¹³ can form and be part of a substituted or unsubstituted cyclic ringhaving from 3 to about 12 carbon atoms; with the proviso that when j is1, T is NR¹⁵R¹⁶), and when j is 2, T is a divalent radical having anitrogen atom directly connected to each carbon atom of the twothiocarbonyl groups; and wherein R¹⁵ and R¹⁶, independently, is the sameor different, optionally substituted, optionally contains heteroatoms,and is hydrogen; or a linear or branched alkyl having from 1 to about 18carbons; or an aryl group or an aryl alkyl group having from 6 to about18 carbon atoms, optionally saturated or unsaturated; or an arylalkylhaving from 7 to about 18 carbons; or an alkenealkyl having from 3 toabout 18 carbon atoms; or derived from polyalkylene glycol ether; orderived from an amine; or R¹⁵ and R¹⁶ are in the form of a substitutedor unsubstituted cyclic ring with the nitrogen atom having a total of 4to about 12 carbon atoms.
 26. A method according to claim 25, whereinsaid haloform is utilized in an amount from 0 percent to about 500percent molar excess and said ketone is used in an amount from 0 percentto about 300 percent molar excess, based on the molar amount of saidmetal salt of said dithiocarbamate.
 27. A method according to claim 26,wherein said R¹² and R¹³, independently are a phenyl group, or an alkylgroup having 1 to about 10 carbon atoms, or wherein R¹² and R¹³ are partof said cyclic ring, and R¹⁵ and R¹⁶, independently, are a phenyl group,an alkyl group having from 1 to about 10 carbon atoms, or hexamethylene,or wherein R¹⁵ and R¹⁶ are part of said cyclic ring.
 28. A methodaccording to claim 22, further comprising the step of reacting at leastone vinyl-containing monomer, or at least one conjugated diene monomerin the presence of said dithiocarbamate compound.
 29. A method accordingto claim 26, wherein said haloform is utilized in an amount from about50 percent to about 200 percent molar excess and wherein the ketone isutilized in the reaction in an amount from about 100 percent to about1000 percent molar excess based on the molar amount of said metal saltof said dithiocarbamate.